Untersuchung von Kobalt(II)-Komplexen mit N-Arylthioharnstoffen

The complexes of cobalt(II) chloride with o, m, p-tolyl thiourea (I–III); m, p-nitrophenyl thiourea (IV, V); o, m, p-hydroxy phenyl thiourea (VI–VIII); m, p-bromophenyl thiourea (IX, X); p-iodophenyl thiourea (XI) and o-bromo-p-methyl phenyl thiourea (XII) have been synthesised. The elemental analysis reveals that ligands (I–V) form bis and the rest forms tris complexes with cobalt(II). Infrared and farinfrared spectral measurements prove that sulphur is taking part in co-ordination. All complexes are nonelectrolytes in acetone as revealed by conductivity measurements. The data obtained from magnetic susceptibility measurements, electronic spectra in solution are consistant with a practically tetrahedral symmetry.     

Zinc-Mediated Facile and Efficient Chemoselective S-Alkylation of 5-Aryl-1,3,4-oxadiazole-2-thiols in the Absence of Base

Zinc-mediated facile and efficient chemoselective S-alkylation of 5-aryl 1,3,4-oxadiazole-2-thiols in the presence of a catalytic amount of tetra butyl ammonium iodide was described. The reaction was performed under neutral conditions. The chemoselectivity of the alkylation was confirmed by NMR spectroscopy and x-ray crystallography.     

p-Tolyl isocyanate derivatization for analysis of CWC-related polar degradation products by mass spectrometry

Most of the precursors and/or degradation products related to the Chemical Weapons Convention (CWC) are polar. Identification of these molecules in environmental samples provides clues regarding the alleged usage and/or synthesis of the parent toxic chemicals. Such polar compounds need to be derivatized in order to analyze them by gas chromatography–mass spectrometry (GC–MS). In this study, we developed a new derivatizing reagent, para-tolyl isocyanate (PTI), for derivatization of polar CWC-related compounds. The PTI reagent selectively derivatizes the –OH and/or?SH functional groups with high efficiency, but does not react with carboxylic acid (?COOH) or phosphonic acid (?(O)P(OH)₂) groups. The PTI derivatives of dialkyl aminoethanols, dialkyl aminoethanol-N-oxides, and 3-quinuclidinol were successfully eluted through GC, and their electron ionization (EI) mass spectra were distinct and provided the structure information by which the isomeric compounds can be easily distinguished. We also calculated the GC-retention index values that can be used for further confirmation of the target compounds. All the studied PTI derivatives can be analyzed by EI-MS with direct insertion probe and/or by direct electrospray ionization mass spectrometry (ESI-MS) together with the MS–MS data; both sets of data provide full structure information. The PTI reagent was found to be better in some respects than the conventional bistrimethylsilyl trifluoroacetamide (BSTFA), a trimethyl silylating reagent. The PTI reagent is commercially available, and the PTI derivatives are highly stable for months and are not sensitive to moisture. The applicability of the PTI derivatization for trace-level determination of the target CWC-related polar compounds in environmental matrices and in human plasma samples is also evaluated.

Development of Polar Organic Mode Chromatographic Method by Polysaccharide-Based Immobilized Chiral Selector and Validation for the Determination of the Enantiopurity of Novel Mineralocorticoid Receptor Antagonist Atropisomer–Esaxerenone

Esaxerenone is a new nonsteroidal mineralocorticoid receptor antagonist utilized to treat high blood pressure. Chemically, esaxerenone is a pyrrole derivative consisting of hindered rotation, which results in stereoisomers named atropisomers. Currently, no methods exist for the separation and quantification of these atropisomers. A new and accurate chiral liquid chromatographic technique was developed and validated to estimate the enantiomeric purity of esaxerenone. Polar organic chiral separation was carried out on an immobilized amylose-based chiral stationary phase (Chiralpak IG) with methanol:acetonitrile:diethylamine (9:1:0.1, v/v/v) mixture as a mobile phase. The total runtime was 15 min, and the resolution (R_s) between the atropisomers was more than 3.0. The detection and quantification thresholds for the R-atropisomer were found to be 0.03 and 0.1 µg mL^?1, respectively, for a test concentration of esaxerenone (1000 µg mL^?1). Over the range from the limit of quantification to 0.3 percent, the method's linearity for the R-atropisomer was excellent (R²?>?0.999). The R-atropisomer recovery varied from 95 to 102%, confirming the method’s good accuracy. For a 48-h research period, the chemical was shown to be stable.

     

Design,synthesis, and biological activity studies of a new class of sulfonated aurones: First synthesis of acidoaurone isolated from Phyllanthus acidus

A novel series of aurones were designed by introducing sulfonic acid group on ring-A and ring-B of known natural aurones such as hispidol, sulfuretin, maritimetin, and aureusidin. These sulfonated aurones were synthesized by a unique approach. Sulfonation on ring-A or ring-B converts water-insoluble aurones into highly water-soluble aurones. The sulfonated aurones were tested for their antioxidant, antiinflammatory, and AChE inhibition activities along with their natural aurones. Ring-A sulfonated aurones displayed higher antioxidant activity, 5-LOX, and AChE inhibition in comparison with their corresponding natural aurones. Ring-B sulfonated aurones exhibited potent 5-LOX inhibitory activity and significant antioxidant activity. Acidoaurone, a first sulfonated aurone isolated from Phyllanthus acidus was synthesized for the first time and was well characterized using NMR, LC–MS, and further confirmed by HMBC.     

On Zagier’s cusp form and the Ramanujan τ function

Zagier constructed a cusp form for each weightk of the full modular group. We use this construction to estimate Fourier coefficients of cusp forms. In particular, we get a non-trivial estimate, by elementary methods and indicate a relationship with the Lindelof hypothesis for classical Dirichlet L-functions. Dedicated to the memory of Professor K G Ramanathan     

Synthesis and ion-exchange properties of zirconium molybdoarsenate (ZrMAs)

Zirconium molybdoarsenate (ZrMAs), an inorganic ion exchanger, has been synthesized and the suitable conditions to separate cesium-137 from fission products waste solution are suggested.     

Aberration-corrected catadioptric magnifiers useful for simple microfiche readers

The present paper considers the magnifying power and aberration properties of three different catadioptric magnifying systems useful for application as simple hand-held microfiche readers. These are in the form of a plano-convex lens, a meniscus lens and an achromatic doublet lens and all their outer surfaces have been coated with a semi-reflecting film so that they behave like catadioptric elements. These can be designed to give magnification in the range of 15 × to 25 × with sufficient eye relief. Using such magnifiers, it is possible to read microfiche having frame sizes of 16 × 12 mm and 12 × 9 mm. The cemented achromatic doublet coated on the outer surfaces seems to give a very good image for use in microfiche reader.     

Determination of trace elements in rocks by optical emission spectroscopy: A new method of internal standardization

Summary A method has been described for the determination of twelve trace elements (Pb, Sn, Cr, Co, Ni, V, Y, La, Zr, Cu, Zn, Sc) in different types of rocks using optical emission Spectroscopy (OES). The method employs a single set of synthetic standards for analysing any type of rock, basic, acidic or intermediate. When an external element, such as osmium, has been added to serve as internal standard, the analytical data showed poor precision. A new method of internal standardization has, therefore, been attempted. In this, a line due to silicon whose intensity is influenced by two adjacent Fe lines, has been used as the internal standard. Such an approach gave better presision (expressed in terms of coefficient of variation). Six international rock standards have been analysed and the data obtained have been compared with that previously reported.

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Bestimmung von Spurenelementen in Gesteinen durch optische Emissions-Spektroskopie: Ein neues Verfahren zur inneren Eichung

Zusammenfassung Zwölf Spurenelemente (Pb, Sn, Cr, Co, Ni, V, Y, La, Zr, Cu, Zn, Sc) werden in verschiedenen Gesteinstypen bestimmt. Basische, saure und intermediäre Gesteine können mit einem einzigen Satz synthetischen Standards analysiert werden. Bei Benutzung eines externen Elements (Os) zur Eichung wurden schlechte Ergebnisse erhalten. Bei dem neuen Verfahren wird eine bessere Reproduzierbarkeit (ausgedrückt als Variationskoeffizient) durch Verwendung einer Siliciumlinie, die durch benachbarte Eisenlinien beeinflußt wird, erzielt. Sechs internationale Standardgesteinsproben wurden nach diesem Verfahren untersucht und die Ergebnisse mit früher erhaltenen verglichen.