2-Nitrodiphenylamine as a versatile high-potential reversible oxidation-reduction indicator

The use of 2-nitrodiphenylamine as a reversible indicator has been investigated in the titration of iron(II) with cerium(IV) sulphate, potassium dichromate and sodium vanadate in sulphuric acid media. Accurate results can be obtained with cerium(IV) sulphate in 0.5–5.0 M acid, with potassium dichromate in 5.0–7.0 M acid, and with sodium vanadate in 5.0–7.5 M acid. With cerium(IV) sulphate the titrations are preferably conducted in 2.0 M sulphuric acid or in a 1.0 M. sulphuric acid-1.0 M pechloric acid medium. Tungstic acid, acetic acid, arsenic(III) and manganese(II) do not interfere. In titrations of iron(II) with dichromate and vanadate, the colour changes at the end-point are much more vivid with 2-nitrodiphenylamine than with ferroin.     

Study of non-isothermal crystallization of amorphous Cu<Subscript>50</Subscript>Ti<Subscript>50</Subscript> alloy

The crystallization kinetics of amorphous Cu₅₀Ti₅₀ has been studied using differential scanning calorimetry (DSC) under non-isothermal conditions. The curves at different linear heating rates (2, 4, 8 and 16 K min^–1) show sharp crystallization peaks. The crystallization peak shifts to higher temperatures with increasing heating rate. The Kissingers method of analysis of the shift in the transformation peak is applied to evaluate the activation energy (E _c). The KJMA formalism, which is basically developed for isothermal experiments, is also used to obtain E _c and the Avrami parameter (n).The DSC data have been analysed in terms of kinetic parameters, viz. activation energy (E _c), Avrami exponent (n) and frequency factor K ₀ using three different theoretical models. It is observed that the activation energy values derived from KJMA approach and modified Kissinger equation agree fairly well with each other. The activation energy values obtained from normal Kissinger method, and Gao and Wang expression underestimate the activation energy.The financial support provided by All India Council for Technical Education (AICTE), New Delhi (Govt. of India) is gratefully acknowledged.     

Energy dispersive X-ray fluorescence (EDXRF) determination of lanthanides after preconcentration on 1-(2-pyridylazo)-2-naphthol modified naphthalene

A method is described for the simultaneous multielement determination of yttrium and lanthanides at microgram level. This is based on the preconcentration of these lanthanides on to 1-(2-pyridylazo)-2-naphthol (PAN) modified naphthalene. The optimal conditions for quantitative preconcentration viz., pH, amount of PAN modified naphthalene, time of stirring and aqueous phase volume were systematically evaluated. The quantitation of lanthanides was carried out by energy dispersive X-ray fluorescence analyzer, employing²⁴¹Am annular source, via their characteristic K X-rays. The developed procedure gave reliable results in the analysis of xenotime samples.     

Identification of radicals spin-trapped in autoxidized linoleic acids: A high performance liquid chromatography and electron spin resonance study

Radicals generated in linoleic acid and deuterated linoleic acid have been trapped by the spin trap 2-methyl-2-nitroso-propane (MNP) and identified by electron spin resonance (ESR) and ENDOR spectroscopy. The formation of two distinct secondary alkyl radical adducts (one conjugated, the other non-conjugated, as shown by their UV absorption spectra) was demonstrated by 11, 11-dideuterio-9-cis-12-cis-linoleic acid using HPLC and ESR spectroscopy.     

Ferrimetric determination of uranium using rhodamine 6G as fluorescent indicator

Experimental conditions have been developed for the titration of uranium^IV with iron^III alum solution, using Rhodamine 6G as a fluorescent indicator. The titration is best carried out at 98–100° in a 2–3N hydrochloric acid medium, under filtered ultraviolet light, using 2.0 ml of 0.05% Rhodamine 6G solution for 30 ml of the titration mixture. A slight excess of iron^III solution quenches the greenish-yellow fluorescence of the dye through inner filter action. With the titration assembly described here, it is possible to determine uranium^IV with an accuracy of about 0.4%. This method appears to be more convenient than the potentiometric titration or the method employing potassium thiocyanate as internal indicator.

Evidence is also presented to show that the reaction between uranium^IV and iron^III is slow at room temperature.     

Biligand metal chelates of 1,10-phenanthroline and several salicyclic acid derivatives in solution

Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO₄], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present.     

Spectrophotometric methods for the determination of tamoxifen citrate

Three simple and sensitive spectrophotometric methods for the determination of tamoxifen citrate have been developed. They are based on the formation of an ion-association complex between the drug and a dye, Erioglaucine A, which is extractable into chloroform and has an absorption maximum at 625 nm (method A), oxidation with excess potassium permanganate and the determination of unconsumed permanganate using Fast Green FCF (method B), or by the formation of a coloured cobalt thiocyante coordination complex which is extracted into benzene and measured at 635 nm (method C). Beer's law limits for methods A, B, and C are 0.5-3.0 mug ml(-1), 1.0-6.0 mug ml(-1) and 100-500 mug ml(-1), respectively. No interference was observed from tableting additives and the applicability of the methods was examined by analysing tablets containing tamoxifen. The quantities determined were 99.0-100.03% of the exptected values.     

The isolation and structure of 6″-bromo-isoarboreol - the first bromine containing lignan

A new lignan from $\text{Gmelina arborea}$ is shown to be 1, 2a-dihydroxy-2e-piperonyl-6e-(6″-bromopiperonyl)-3, 7-dioxabicyclo-[3,3,0]-octane, the first example of a bromine containing lignan.     

RED EDGE EXCITATION EFFECT IN INTACT EYE LENS

Shift in the wavelength of emission upon shift in the excitation wavelength towards the red edge of the absorption band is termed Red Edge Excitation Shift (REES). This effect is observed only in situation where the fluorophore mobility with respect to the surrounding matrix is considerably reduced. We have observed such red edge excitation effect in the intact eye lens. The REES observed for a normal lens is different from that seen in a photodamaged lens and hence appears to be a potential tool to monitor the changes in the state of the lens. Photodamage experiments with tryptophan in polyethylene glycol (PEG) and intact eye lens indicate that the red edge photon can also cause photodamage.     

Semi-synthesis of paclitaxel from naturally occurring glycosidic precursors

Paclitaxel, an antitumor drug effective on ovarian and breast carcinomas, is currently being produced both by direct isolation from the bark of Taxus brevifolia and by semi-synthesis from a natural precursor, 10-deacetyl baccatin III. Although other potential precursors such as 10-deacetyl paclitaxel-7-xyloside were known since 1984, their conversion to paclitaxel could not be achieved because of the lack of suitable methodology for hydrolyzing the xylose residue, compatible with the stability of the compound. A method is described here using periodate, followed by phenylhydrazine, to effect deglycosidation of 10-deacetyl paclitaxel-7-xyloside to form 10-deacetyl paclitaxel. In addition, by including an intermediate acetylation step before the reaction with phenylhydrazine, “direct” conversion of this xyloside to paclitaxel itself, is described. Because 10-deacetyl paclitaxel-7-xyloside occurs at >0.1% in the bark of Taxus brevifolia, its successful hydrolytic conversion to paclitaxel represents an extremely important reaction for the enhanced availability of this drug.