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.     

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.     

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.     

Graft polymers from poly(vinyl chloride) and chlorinated rubber

Graft polymers from poly(vinyl chloride) (PVC) and chlorinated rubber (CIR) with side chains of poly(methyl methacrylate) (PMMA), poly(methyl acrylate) (PMA), or poly(ethyl methacrylate) (PEMA) were synthesized. For this purpose, a vinyl monomer was polymerized in the presence of small quantities of PVC or CIR with benzoyl peroxide as catalyst. The graft polymers were separated from both homopolymers by precipitation with methanol from methyl ethyl ketone solutions of the reaction products and the grafting efficiency was calculated. The graft polymers were characterized by infrared spectra, elemental analysis, NMR, and osmometric or light-scattering determinations. From the results it is concluded that the PVC or CIR molecules contain side chains of PMMA, PMA, or PEMA. The graft polymers showed higher molecular weights, and the values of second virial coefficient for these polymers were much different from those of the starting polymers.     

Photoacoustic spectroscopy of solids and surfaces

After briefly reviewing the theory and instrumentation, results from a variety of experiments carried out by the authors on the photoacoustic spectroscopy of solids and surfaces by employing an indigenous spectrometer are discussed in the light of the recent literature. Some of the important findings discussed are, phase angle spectroscopy, anomalous behaviour of monolayers, unusual frequency dependence in small cell volumes, spectra of a variety of solids including amorphous arsenic chalcogenides, photoacoustic detection of phase transitions and determination of surface areas and surface acidities of oxides. Recent developments such as piezoelectric photoacoustic spectroscopy, depth profiling and subsurface imaging are also presented. Contribution No. 124 from the Solid State and Structural Chemistry Unit.     

Determination of trace levels of titanium in polyolefin polymers by catalytic reduction using square wave voltammetry

A sensitive and rapid method for the determination of trace levels of titanium in polyolefin polymers using square wave voltammetry is discussed. It involves ashing, acid digestion of polymer samples and determination of titanium(IV) by catalytic reduction using square wave voltammetric (SWV) technique. A well defined peak of titanium(IV) in Britton-Robinson buffer solution containing EDTA and KBrO(3) is observed in the potential range of -0.10 to -0.40 vs. Ag/AgCl. Calibration graphs were linear in the range 0.05-0.25 microg/ml for titanium. Effects of pH and concentration of bromate, EDTA and buffer constituents are studied for the optimization of experimental conditions. Interference from other concomitants present in the polymer matrix are studied. Low density polyethylene (LDPE) obtained by tubular process was used for preparing the synthetic standards in order to optimize the experimental conditions and good recoveries (99-101%) were obtained. The method was extended to different polyolefin samples and the results obtained for the titanium content compared with those obtained by UV/Vis spectrophotometry. Statistical evaluation showed no significant bias between the two methods. SWV is found suitable for the estimation of Ti in the range 1-50 microg/g in polyolefin polymers with a RSD < 2.0%.     

Kinetics of oxidation of isopropanol by IO4? catalyzed by metal ions

The kinetics of oxidation of isopropanol (IPA) by IO ₄ ^– in the presence of Os(VIII), Ru(III) and mixture of Os(VIII) and Ru(III) has been studied. The catalytic effect was found to be in the order Os(VIII)

IO ₄ ^– Os(VIII), Ru(III) Os(VIII) Ru(III), . : Os(VIII)     

Oxygen promoted radical polymerization of acrylonitrile in aqueous nitric acid. A kinetic study

The polymerization of acrylonitrile (AN) initiated by oxygen-ascorbic acid (AA)-ferric ion system was studied in dil. HNO₃ at 40°. The rate of polymerization, R_p, was found gravimetrically. In the [Fe³⁺] range, (2–5 × 10^?5 M, R_p was proportional to [AN]^{1.5 ± 0.05}, [O₂]^{0.5 ± 0.02} [AA]⁰ and [Fe³⁺]⁰; for [Fe³⁺] = (5–30) × 10^?5 M, it was proportional to [AN]^{1.8 ± 0.05}, [O₂]^{0.6 ± 0.02}, [AA]⁰ and [Fe³⁺]^{?0.9 ± 0.05}. A plausible reaction scheme is proposed and rate law presented to explain these results. R_p increased with ionic strength and [HNO₃] (up to ～0.25 M). An initial rate increase with temperature followed by a decrease was noticed. Chain lengths of the polymers were determined viscometrically.     

PHOTOREDUCTION OF SOME NITROBIPHENYL ETHER HERBICIDES TO NITRO RADICAL ANIONS BY β-CAROTENE AND RELATED COMPOUNDS

Abstract —The nitrobiphenyl ether herbicides; 4-nitrobiphenyl ether, bifenox, nitrofen, acifluorfen, acifluorfen-methyl, acifluorfen-ethyl, and oxyfluorfen were reduced to their corresponding nitro radical anions by visible light in the presence of β-carotene, lycopene, retinol, retinal, retinoic acid and retinyl acetate in anaerobic solutions at high pH. It was more difficult to obtain spectra of bifenox, nitrofen and oxyfluorfen than acifluorfen derivatives, probably due to their poor solubilities. In neutral solutions the steady-state concentration of the nitro radical anions was low due to their faster rate of dispropor-tionation and the poor solubility of β-carotene. In the presence of retinal, the nitro radical anion of acifluorfen was produced at pH 7.4. Compounds containing conjugated double bonds such as crotonaldehyde and 2.4-hexadienal also reduced acifluorfen and its derivatives to their respective nitro radical anions in the presence of light. Ubiquinone-50 which does not contain conjugated double bonds in the side chain did not reduce acifluorfen under similar conditions.