MECHANISM OF PHOTOREDUCTION OF THIAZINE DYES BY EDTA STUDIED BY FLASH PHOTOLYSIS-II. pH DEPENDENCE OF ELECTRON ABSTRACTION RATE CONSTANT OF THE DYES IN THEIR TRIPLET STATE

Abstract— The pH dependence of the apparent reactivity of thiazine dyes in their triplet states has been studied in aqueous solutions, using as electron donor HY^-3, the trianionic species of ethylene diamine tetraacetic acid (EDTA), in the pH range 4–8. The pH dependence is found to be related to a change in the degree of protonation of the triplet excited dye. The apparent reactivity and lifetime of two differently protonated forms of thionine, azur B and methylene blue were determined by classical and dye-laser flash techniques, making it possible to evaluate the rate constant for electron abstraction of these molecules in their triplet states. It is found that: (a) protonation on the ring nitrogen increases the electron-abstraction rate constant of the triplet-state species about twenty-fold, and (b) methylation on the side amino groups decreases it.     

Magnetic behavior of amorphous Fe−Ni−Zr alloys and their response to radiation damage

The magnetic properties of two amorphous Fe?Ni?Zr alloys, Fe_89.7Ni_0.03Zr₁₀ and Fe₇₀Ni₂₀Zr₁₀, both in the “as cast” and neutron irradiated states were investigated by Mössbauer spectroscopy and dc magnetic susceptibility measurements. The upper magnetic ordering temperatures of Fe_89.7Ni_0.03Zr₁₀ are 232K and 246K for the “as cast” and irradiated samples, respectively. The magnetic ordering temperature for Fe₇₀Ni₂₀Zr₁₀ was about 478K for both the “as cast” and irradiated samples. Both compositions yield magnetic hyperfine spectra, which show a considerable relaxation effect that must be explicitly considered in the calculation of the average local Fe moments. When this is done, these values derived from Mössbauer spectra are in good agreement with the dc susceptibility values. The effects of neutron irradiation on the magnetic properties of these alloys are small.     

Inhibition of corrosion of commercial mild steel in presence of tetrazole derivatives in acid medium

The inhibitive influence of tetrazole derivatives namely, 1-(9¹-acridinyl)-5-(4′-aminophenyl) tetrazole, 1-(9′-acridinyl)-5-(4′-hydroxy phenyl) tetrazole and 1-(9′-acridinyl)-5-(4′-chlorophenyl) tetrazole on the corrosion of commercial mild steel in 1 N hydrochloric acid medium was studied by weight loss method. The monolayer adsorption has been confirmed by fitting the data to the Langmuir adsorption isotherm. Weight loss studies have been carried out at 303K, 318K and 333K. Thermodynamic parameters like heat of adsorption, activation energy and free energy change have been calculated. The maximum inhibition of efficiency of tetrazole derivatives, 1-(9′-acridinyl)-5-(4′-amoinophenyl) tetrazole, 1-(9′acridinyl)-5-(4′-hydroxyphenyl) tetrazole and 1-(9′-acridinyl)-5-(4′-Chlorphenyl) tetrazole was found to be 60.59%, 89.00% and 92.74, respectively. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Inhibition of corrosion of aluminium in presence of fluorescein in basic medium

The influence of Fluorescein in conjunction with calcium oxide on the corrosion of Aluminium in 1.0 N NaOH was studied by galvanostatic studies and weight loss studies. It has been found that the inhibition of corrosion of aluminium increased with the increasing concentration of the inhibitor. The maximum inhibition efficiency of fluorescein alone was found to be 30.80%. However, the addition of calcium oxide increased the maximum inhibition efficiency to 53.71%. The corrosion process was found to be under the anodic control, in the presence or in the absence of inhibitor. The inhibition was found to be mixed type. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, Inida, Nov. 28–30, 2003.     

The57Fe magnetic hyperfine field in Au-Fe alloys (evidence favoring the two Fe-environment model of Au-Fe alloys)

Conclusions The results of our analysis strongly support our two Fe environment hypothesis. The critical concentration at about 12 at.% suggests that the dependence of H(0,x) on x undergoes a fundamental change at this concentration. Furthermore, the so-called critical concentration at about 17 at.% apparently has little to do with any fundamental alloy property. Rather, it reflects the 12 at.% critical composition when properties are analyzed in terms of the average rather than the local Fe concentration. The two Fe environments appear to have differing configurations.This work was performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48.     

PHOTOSENSITIZATION BY ANTIMALARIAL DRUGS

Abstract The antimalarial drugs, chloroquine, hydroxychloroquine, quinine, quinacrine, amodiaquine and primaquine and the local anaesthetic, dibucaine, were tested for in vitro photosensitizing capability by irradiation with 365 nm UV light in aqueous solutions. The ability of these compounds to photosensitize the oxidation of 2,5-dimethylfuran, histidine, tryptophan or xanthine, and to initiate the free radical polymerization of acrylamide was examined in the pH range 2-12. Chloroquine and hydroxychloroquine show maximal photooxidative behaviour when in the monocation form at pH 9, in contrast to quinine which is extremely efficient as the dication below pH 4. This pattern appears to relate to the fluorescence yield as a function of pH. Chloroquine in the monocation or neutral form was found to undergo dechlorination upon irradiation, and this correlates directly with its ability to initiate photo-polymerization of acrylamide. Quinine also gives rise to small polymerization rates, attributed to photo-ionization in the quinoline ring, yielding a cation radical. Amodiaquine, primaquine and quinacrine do not have significant photochemical activity in aqueous solution. Dibucaine exhibits a strong photosensitizing capability at low pH, similar to quinine.