Spectrophotometric determination of palladium after coprecipitation of its 9,10-Phenanthrenequinone monoximate on microcrystalline naphthalene

Summary A spectrophotometric method has been developed for the microdetermination of Pd(II) as its 9,10-Phenanthrenequinone monoximate, by coprecipitation on solid naphthalene and dissolution in chloroform. The method can be applied to the determination of palladium in certain synthetic mixtures.

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Spektrophotometrische Bestimmung von Palladium nach Mitfällung seines 9,10-Phenanthrenchinonmonoximates auf mikrokristallines Naphthalin

Zusammenfassung Ein spektrophotometrisches Verfahren zur Mikrobestimmung von Pd(II) als 9,10-Phenanthrenchinonmonoximat durch Mitfällung auf festes Naphthalin und Lösung in Chloroform wurde ausgearbeitet. Dieses Verfahren eignet sich zur Bestimmung von Palladium in gewissen synthetischen Gemischen.

     

Hydrodechlorination of chlorobenzene over supported metal catalysts

The use of supported Pd catalysts, with low and high metal content, for the hydrodechlorination of chlorobenzene is presented in this article. Application of microwave irradiation during preparation of catalysts resulted in the synthesis of large Pd particles at moderate temperatures. The nature of the support played a key role in the formation of cationic Pd species. The extent of interaction of the Pd species with the support, the nature of metal precursor, particularly the residual chlorine on the surface were found to significantly affect the activity of the catalysts. In the case of bimetallic catalysts also microwave heating resulted in creation of bigger particles of Pd compared to those observed in conventionally heated catalysts. Besides, it minimized alloy formation as a result of which the activity of the catalysts in hydrodechlorination was found to be higher compared to that observed on conventionally prepared catalysts. Contrary to the general observation that low dispersed Pd catalysts are preferable for high stability, by means of the deposition-precipitation method adopted for catalyst preparation it was demonstrated that even highly dispersed (low Pd containing) catalysts can exhibit comparable activity and stability. An analysis of the nature of Pd species and its role in the stability of the catalysts is presented.IICT communication No. 051224     

Lewis acid-assisted olefin cross-metathesis reaction: an efficient approach for the synthesis of glycosidic-pyrroloquinolinone based novel building blocks of camptothecin and evaluation of their antitumor activity

A series of glycosidic-pyrroloquinolinone based novel building blocks of camptothecin (2a–g) were synthesized via Lewis acid-assisted olefin cross-metathesis reaction using Ti(OⁱPr)₄ 30 mol % and 10 mol % of Grubb’s second generation catalyst with good to excellent yields. Most of these compounds exhibited significant growth inhibitory effects on all the tested cancer cell lines and three compounds (2c, 2d and 2e) showed potent cytotoxic activity.     

Synthesis and Antibacterial Activity of New Diaryldiamines

Several new quinolines and quinazolines ( 4, 10, 13 ) have been synthesized from cheap and readily available chemicals through a series of simple chemical transformations. Most of the synthesized compounds have been evaluated for antibacterial activity against Gram positive and Gram negative strains. Some of the synthesized compounds displayed interesting activity but not very promising for further development.     

Adhesion and stress of magnesium oxide thin films: Effect of thickness, oxidation temperature and duration

Nanoscale magnesium oxide thin films have been deposited on glass substrate by thermal oxidation (in air) of vacuum evaporated magnesium films. X-ray diffraction (XRD) showed orientation along (2 0 0) and (2 2 0) directions. The mechanical properties of the MgO thin films were found to be the function of thickness (300, 450 and 600 nm), oxidation temperature (573, 623 and 673 K) and oxidation duration (90 and 180 min). As oxidation temperature and oxidation duration increases, adhesion and intrinsic stress were found to increase. Intrinsic stress decreased whereas adhesion increased due to increase in thin film thickness. The value of intrinsic stress was in range 28.902-73.212 (×10⁷ N/m²) and that of adhesion was 12.1-27.4 (×10⁴ N/m²) for the thin film of thickness 300 nm.     

Preparative high-performance liquid chromatographic separation of naphthodianthrones from St. John's Wort

St. John's Wort (Hypericum perforatum), a perennial flowering plant, has been used medicinally for thousands of years and has most recently been identified as an effective treatment for mild to moderate depression and neuralgic disorders. This work presents a procedure for the isolation of naphthodianthrones from St. John's Wort by an accelerated extraction and separation of marker compounds by preparative high-performance liquid chromatography (HPLC) with photodiode array detection. The accelerated extraction method minimizes the extraction time and increases the yield, and the marker compounds obtained by preparative HPLC are of 98% purity. The compounds are characterized by liquid chromatography-mass spectrometry (electrospray ionization) and NMR spectra.     

Law of the iterated logarithm for perturbed empirical distribution functions evaluated at a random point for nonstationary random variables

We consider perturbed empirical distribution functions , where {Ginn, n1} is a sequence of continuous distribution functions converging weakly to the distribution function of unit mass at 0, and {X _{i, i}1} is a non-stationary sequence of absolutely regular random variables. We derive the almost sure representation and the law of the iterated logarithm for the statistic whereU _n is aU-statistic based onX ₁,...,X _n . The results obtained extend or generalize the results of Nadaraya,⁽⁷⁾ Winter,⁽¹⁶⁾ Puri and Ralescu,^(9,10) Oodaira and Yoshihara,⁽⁸⁾ and Yoshihara,⁽¹⁹⁾ among others.Research supported by the Office of Naval Research Contract N00014-91-J-1020.     

Spectrophotometric determination of iridium(III) and osmium(VIII) with phenanthrenequinone monoxime after extraction into molten Naphthalene

Summary Conditions have been established for the extraction of iridium (III) and osmium(VIII) as their phenanthrenequinone monoximates into molten naphthalene. The naphthalene is allowed to solidify, separated by filtration, dried with filter paper and dissolved in chloroform. The absorbance is measured at 470 nm for iridium and 475 nm for osmium. Beer's law is obeyed in the concentration ranges 3.2–38.6g of iridium and 1.0–10.9g of osmium in 10 ml of chloroform. The molar absorptivities are 2.3×10⁴ and 8.8×10⁴l. mole^–1.cm^–1 for iridium and osmium respectively. The optimum pH range for the extraction is 4.6–7.4 for iridium and 6.8–10.5 tor osmium. Interferences have been studied in detail and the method successfully applied to various synthetic mixtures. The two metals can be determined sequentially (in the absence of interfering ions), osmium first.

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Spektrophotometrische Bestimmung von Ir(III) und O's(VIII) mit Phenanthrenchinonmonoxim nach Extraktion mit geschmolzenem Naphthalin

Zusammenfassung Die Extraktionsbedingungen für Ir(III) und Os(VIII) als Phenanthrenchinonmonoximate mit geschmolzenem Naphthalin wurden ermittelt. Man läßt das Naphthalin erstarren, filtriert es, trocknet es mit Filterpapier und löst es in Chloroform. Die Absorbanz wird bei 470 nm gemessen für Ir und bei 475 nm für Os. Das Beersche Gesetz gilt für Ir im Konzentrationsbereich 3,2–38,6g und für Os zwischen 1,0 und 10,9g/10 ml Chloroform. Die molare Absorption beträgt 2,3×10⁴ bzw. 8,8×10⁴l·mol^–1·cm^–1 für Ir bzw. Os. Das optimale pH-Gebiet für die Extraktion von Ir liegt bei 4,6–7,4, für Os bei 6,8–10,5. Störungen wurden im Detail untersucht und das Verfahren mit Erfolg für verschiedene Gemische angewendet. In Abwesenheit störender Ionen können Osmium und Iridium hintereinander bestimmt werden.