Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Pyridazine derivatives. Part 40: Reactivity of 5-alkynylpyridazin-3(2H)-ones toward hydrochloric acid

5-Alkynylpyridazin-3(2H)-ones or 5-(2-chloroalkenyl)pyridazin-3(2H)-ones were isolated during the cleavage of the methoxymethyl group in a series of 5-alkynyl-2-methoxymethylpyridazin-3(2H)-ones by treatment with hydrochloric acid. The efficient and selective cleavage of the methoxymethyl group in these compounds can be performed under mild conditions by employing aluminium chloride.     

Hydrogen peroxide in basic media for whole blood sample dissolution for determination of its lead content by electrothermal atomization atomic absorption spectrometry

Hydrogen peroxide in basic media is proposed as a means for dissolving whole blood samples to be analyzed by electrothermal atomization atomic absorption spectrometry, ET AAS. Approximately 2 g of the whole blood sample were directly weighed in a 150 mL volumetric flask; 3 mL of a NaOH 0.2 mol L⁻¹ solution, two drops of 1-octanol, as an antifoaming agent, and 1 mL of 30% volume hydrogen peroxide were added to the flask to promote oxidation. The solution was then manually shaken and after approximately three minutes of shaking, a clear solution, with no apparent suspended solids or greasy layers, was obtained. Distilled-deionized water was used to complete the volume. Ten μL of the resulting solution along with 10 μL of a solution containing 5000 mg L⁻¹ of NH₄H₂PO₄ and 300 mg L⁻¹ of Mg(NO₃)₂ as a modifier, were injected into transversely heated graphite tubes for lead determination. Both aqueous standards and standard addition calibration curves produced results not significantly different at a 95% confidence limit level. Accuracy of the measurements was assessed by analysis of the IAEA A-13 (concentration of trace and minor elements in freeze dried animal blood) standard reference material containing 0.18 mg L⁻¹ lead on a dry basis and by means of recovery tests. Analysis of the IAEA A-13 standard produced 0.17 ± 0.02 mg L⁻¹ lead on a dry basis; recovery tests afforded values from 95 to 105%. Ten consecutive measurements of a 5 ppb lead solution gave a characteristic mass of 47.2 pg and a (3S) detection limit of 1.77 μg L⁻¹ Pb. Results obtained from analysis of whole blood samples of volunteer donors covered a lead concentration range between 8 and 21 μg L⁻¹ with a mean value of 11.9 ± 4.7 μg L⁻¹.     

Determination of manganese in brain samples by slurry sampling graphite furnace atomic absorption spectrometry

A simple procedure for the determination of manganese in different sections of human brain samples by graphite furnace atomic absorption spectrometry has been developed. Brain sections included cerebellum, hypothalamus, frontal cortex, vermix and encephalic trunk. Two sample preparation procedures were evaluated, namely, slurry sampling and microwave-assisted acid digestion. Brain slurries (2% w/v) could be prepared in distilled, de-ionized water, with good stability for up to 30 min. Brain samples were also digested in a domestic microwave oven using 5 ml of concentrated HNO₃. A mixed palladium+magnesium nitrate chemical modifier was used for thermal stabilization of the analyte in the electrothermal atomizer up to pyrolysis temperatures of 1300 °C, irrespective of the matrix. Quantitation of manganese was conducted in both cases by means of aqueous standards calibration. The detection limits were 0.3 and 0.4 ng ml⁻¹ for the slurry and the digested samples, respectively. The accuracy of the procedure was checked by comparing the results obtained in the analysis of slurries and digested brain samples, and by analysis of the NIST Bovine Liver standard reference material (SRM 1577a). The ease of slurry preparation, together with the conventional set of analytical and instrumental conditions selected for the determination of manganese make such methodology suitable for routine clinical applications.