14 MeV neutron activation analysis of gold jewellery

Samples of nominal 18 carat and 21 carat gold jewelleries from the local market were non-destructively bulk analyzed using neutron activation analysis. Neutrons of 14 MeV energy were used with a fast pneumatic sample transfer system. The actual gold contents, as well as the composition of the base metals in these samples were determined. The fast neutron activation was found to be an efficient, quick and accurate method of characterizing the precious metal objects routinely in bulk, with a large sample throughput. The results demonstrate the commercial availability of the technique for non-destructive bulk analysis of precious metal objects.     

Adamantane-like cluster complexes of mixed-valent copper-copper and nickel-copper thiolates

Square-planar copper(II) and nickel(II) derivatives of the cis-dithiolate N(2)S(2) ligand bis(N,N'-2-mercapto-2-methylpropyl)-1,5-diazocyclooctane, (bme*daco)M, nucleate four Cu(I)Cl moieties, forming M(II)(2)Cu(I)(4)S(4) clusters with unusual triply bridging thiolates, mu(3)-SR, in the topological form of adamantane. As determined by X-ray crystallography, the (bme*daco)M (M = Cu or Ni) metallothiolate serves as a bidentate ligand that bridges four Cu(I) ions, utilizing all lone pairs on sulfurs. Further characterization by electrochemical and electronic spectral measurements suggests greater electron delocalization in the all-copper complex as compared to the NiCu heterometallic complex. Mass spectral data imply that the mixed-metal Ni(II)(2)Cu(I)(4)S(4) is more stable toward CuCl loss than Cu(II)(2)Cu(I)(4)S(4), a result that is corroborated by extraction of Cu(I) by 1,2-bis(diphenylphosphino)ethane in the latter but not the former.     

Kinetics and mechanism of the photolytic CO-substitutions of cyclopentadienyl(dicarbonyl)iron thiocarboxylate complexes,Cp′Fe(CO)2SCOR (Cp′ = C5H5, ButC5H4,1,3-Bu2tC5H3; R = alkyl,aryl)

The kinetics of the photolytic CO-substitution of CpFe(CO)₂SCOR [Cp = C₅H₅, Bu ^t C₅H₄, 1,3-Bu₂ ^t C₅H₃; R = Me, Bu ^t , Ph, 2-(O₂N)C₆H₄, 3-(O₂N)C₆H₄, 4-(O₂N)C₆H₄, 3,5-(O₂N)₂C₆H₃] with PPh₃ were studied in CH₂Cl₂ at 0 °C by i.r. spectroscopy. The reactions yielded exclusively the mono-CO-substituted derivatives, CpFe-(CO)(PPh₃) SCOR, and were found to follow second order kinetics with first order dependence on the concentration of each reactant. The differences in rates are discussed in terms of current knowledge pertaining to such reactions. An associative mechanism is proposed to account for the kinetic data of the reactions described.     

Base induced cyclization of some quinolines. Formation of fused nitrogen heterocyclic ring system

Condensation of 3,5-dinitro-4-chloro-6-methoxy-2-methylquinoline (1) with benzylamine, ethanolamine and/or thioglycolic acid afforded the quinoline derivatives4 a-c. Cyclization of4 a and4 b with alkali and condensation of1 with glycine in sodium carbonate solution furnish 2H-imidazo[4,5-c]quinoline derivatives5 a-c, respectively. Treatment of5 b with benzaldehyde in presence of zinc chloride gave the styryl derivative6. 1 reacted with sodium azide to give the azido derivative4 d, which upon treatment with phenylhydrazine or sodium borohydride yielded the 4-amino derivative4 3. Moreover,1 was treated with phenylhydrazine to give4 f, which cyclized in 10% sodium hydroxide solution to the corresponding v-triazolo[4,5-c]quinoline 3-oxide derivative7. When however4 f was treated with dilute hydrochloric acid, the corresponding phenylpyrazolo[3,4,5-de]quinoline derivative8 was obtained.

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Baseninduzierte Cyclisierung einiger Chinoline. Darstellung höherer Stickstoff-Heterocyclen

Zusammenfassung Kondensation von 3,5-Dinitro-4-chlor-6-methoxy-2-methylchinolin (1) mit Benzylamin, Ethanolamin und/oder Thioglycolsäure ergab die Chinolinderivate4 a-c. Cyclisierung von4 a und4 b mit Alkali und Kondensation von1 mit Glycin in Natriumcarbonatlösung lieferte 2H-imidazo[4,5-c]chinolin-Derivate5 a-c. Behandlung von5 b mit Benzaldehyd in Gegenwart von Zinkchlorid ergab das Styrylderivat6. 1 wurde mit Natriumazid zum Azidoderivat4 d umgesetzt, das mit Phenylhydrazin oder Natriumborhydrid zum 4-Aminoderivat4 e weiterreagierte.1 ergab mit Phenylhydrazin4 f, das in 10% NaOH-Lösung zum entsprechenden Triazolo[4,5-c]chinolin-Derivat7 cyclisierte. Aus4 f wurde mit verdünnter Salzsäure das Phenylpyrazolo[3,4,5-de]chinolin8 erhalten.

     

Membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene–perfluorovinyl ether)

Some properties of the membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene-perfluorovinyl ether) copolymer (PFA) films have been investigated. The dimensional change caused by grafting and swelling behavior, water uptake, electrical conductivity, and mechanical properties of the grafted films were found to increase as the grafting proceeds. The influence of the preparation conditions (such as preirradiation dose, monomer concentration, grafting temperature, and film thickness) on those properties was studied. These properties were found to be dependent mainly on the degree of grafting regardless of grafting conditions, except at higher monomer concentration (>40 wt %). The electric conductivity and mechanical properties for the membranes obtained at higher AAc concentrations were lower than those obtained at lower ones. Analysis by x-ray microscopy of the grafted films revealed that the grafting begins at the part close to the film surface and proceeds into the central part with progressive diffusion of monomer to give finally homogeneous distribution of the electrolytes in the whole bulk of the polymer. The membranes show good electrochemical and mechanical properties which make them acceptable for practical use as cation-exchange membranes.     

Effect of an admixture on the electrical and thermal properties of triglycine sulphate crystals

The influence of chloroacetic acid amide (AC) on the temperature-dependence of the electrical conductivity (), thermal expansion (_ij) and specific heat ((C _p) of triglycine sulphate crystals was studied in the phase transition range (T _c=49°). The addition of isostructural AC increased the electrical conductivity, decreased the thermal expansion and changed theC _p peak. The mechanism is discussed on a thermodynamic basis.

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Zusammenfassung Der Einfluß der Zumischung von Chloressigsäureamid (AC) auf die Temperaturabhängigkeit der elektrischen Leitfähigkeit, der Wärmeausdehnung _ij und der spezifischen WärmeC _p von Triglycinsulfat-Kristallen wurde im Phasenübergangsgebiet (T _c=49 °C) untersucht. Die Beimischung von isostrukturellem AC erhöht die elektrische Leitfähigkeit und vermindert die Wärmeleitfähigkeit, während derC _p-Peak verändert wird. Der Mechanismus kann thermodynamisch diskutiert werden.

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(), () _ij) () , T _c=49°. , , , , C _p. .

     

Comparative studies on the adsorption and association of 3-methylxanthine and 7-methylxanthine at a charged interface

Summary A systematic comparative study of the adsorption and association of 3-methylxanthine (3MXan) and 7-methylxanthine (7MXan) at mercury-solution interfaces in acidic, neutral, and alkaline buffer solutions was undertaken by ac voltammetry. At bulk concentrations of3MXan above a threshold value, the stacking interactions between vertically oriented molecules lead to a slow reorientation aroundE _ecm, and the molecules adopt a perpendicular orientation. The association of the adsorbed molecules of7MXan is hindered and is not effective in promoting base-base stacking interactions. The enhanced surface activity of3MXan compared to7MXan results from the different position of the methyl group in the purine moiety. The effect of some divalent metal ions on adsorption stages and association of the investigated compounds has been studied. The results indicate that the complexation of methylated xanthine enhances the stacking interactions and hence would be expected to facilitate the formation of perpendicularly stacked layers ofM(II)-MXan complexes on the electrode surface. The adsorption parameters of the investigated compounds have been computed in absence and presence of Cu(II) at differentpH values. The results are compared with the behaviour of xanthine.

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Vergleichende Untersuchungen zur Adsorption und Assoziation von 3-Methylxanthin und 7-Methylxanthin an einer geladenen Grenzfläche

Zusammenfassung Eine systematische vergleichende Untersuchung zur Adsorption und Assoziation von 3-Methylxanthin (3MXan) und 7-Methylxanthin (7MXan) an Quecksilber-Lösungs-Grenzflächen wurde mittels AC-Voltammetrie in sauren, neutralen und basischen Pufferlösungen durchgeführt. Oberhalb einer bestimmten Grenzkonzentration kommt es durch Wechselwirkungen zwischen vertikal angeordneten3MXan-Molekülen zu einer langsamen Reorientierung umE _ecm, was zu einer senkrechten Anordnung führt. Die Assoziation von7MXan ist gehindert und erlaubt daher keine ausgeprägten Basen-Basen-Wechselwirkungen. Die erhöhte Oberflächenaktivität von3MXan gegenüber7MXan resultiert aus der unterschiedlichen Stellung der Methylgruppe am Purinrest. Der Effekt einiger zweiwertiger Metallionen auf die Adsorption und Assoziation von3MXan und7MXan wurde untersucht. Die Ergebnisse weisen auf eine Begünstigung der Wechselwirkungen hin; die Bildung von vertikal angeordneten Grenzschichten an der Elektrodenoberfläche sollte daher im Fall vonM(II)-Mxan-Komplexen erleichtert sein. Die Adsorptionsparameter der untersuchten Verbindungen wurden in Abwesenheit und in Gegenwart von Cu(II) bei verschiedenenpH-Werten berechnet. Die Ergebnisse werden mit dem Verhalten von Xanthin verglichen.

     

Decomposition of vegetables for determination of Zn,Cd, Pb and Cu by stripping voltammetry

A simple and accurate digestion method using nitric acid, perchloric acid and hydrogen peroxide has been developed for use in trace analysis for heavy metals in vegetables by differential pulse anodic stripping voltammetry. The recovery of the metals from the samples is lower if the hydrogen peroxide is omitted from the digestion mixture. Standard reference materials have been analysed satisfactorily by this method.     

Determination of camptothecin in biological fluids using reversed-phase high-performance liquid chromatography with fluorescence detection

Camptothecin, a plant alkaloid with antitumor activity, is a potent and rapidly acting inhibitor of DNA synthesis. The objective of this study was to develop a sensitive high-performance liquid chromatographic (HPLC) method for the detection and estimation of the camptothecin concentration in biological fluids. Using HPLC coupled with fluorescence detection, at an excitation wavelength of 370 nm and an emission wavelength of 434 nm, we found that the lower limits of detection for camptothecin in aqueous, plasma and urine samples were 0.5, 1 and 10 ng/ml, respectively. The ideal mobile phase used was methanol-10 mM potassium phosphate (75:25, v/v, pH 4.0). To determine the utilization of the method in a biological system, we studied the pharmacokinetics of camptothecin in mice. Elimination of camptothecin from mice blood was triphasic and followed first-order kinetics. The half-life of camptothecin in mouse blood was 25.7 min. Our studies indicate that HPLC with fluorescence detection for the determination of camptothecin in different media is a simple, rapid, sensitive and reproducible method.     

Dichotenone-a and -b: two new enones from the marine brown alga Dictyota dichotoma (Hudson) Lamour

Marine brown alga Dictyota dichotoma (Dictyotaceae) collected from Karachi coast of Arabian Sea yielded two new (1 and 2) enones (dolastane-diterpenoids) named: dichotenone-A and -B along with an olide (loliolide, 3) as a new source. Their structures have been characterized with the aid of 2D-NMR spectroscopic techniques.