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.     

Synthesis of N-(tosyl)azetidin-2-imines

A synthetic route for N-(tosyl)azetidin-2-imines $\text{6}$, a novel class of derivatives of β-lactams, has been developed. The procedure is applicable to the synthesis of azetidin-2-imines related to penicillins and cephalosporins.     

Column selection and method development for the separation of nucleoside phosphotriester diastereoisomers, new potential anti-viral drugs. Application to cellular extract analysis

Analytical HPLC methods using derivatized cellulose and amylose chiral stationary phases used in normal and reversed-phase modes were developed for the diastereoisomeric separation of mononucleotide prodrugs (pronucleotides) of 3'-azido-2',3'-dideoxythymidine (AZT). The resolutions were performed with two silica-based celluloses using normal and reversed-phase methodologies: Tris-3,5-dimethylphenylcarbamate (Chiralcel OD-H and Chiracel OD-RH) and Tris-methylbenzoate (Chiralcel OJ and OJ-R). Two amyloses phases, Tris-3,5-dimethylphenylcarbamate (Chiralpak AD) and Tris-(S)-1-phenylethylcarbamate (Chiralpak AS), were used in normal-phase mode. Additionally, we developed separation using two stationary phases with immobilized cyclodextrins in reversed-phase and polar-organic modes. The mobile phase and the chiral stationary phase were varied to achieve the best resolution. Different types and concentration of aliphatic alcohols, acetonitrile or water in the mobile phase were also tested for the different separation modes. An optimal baseline separation (Rs > 1.5) was readily obtained with all silica-based celluloses and amyloses using a normal-phase methodology. The different columns gave complementary results in term of resolution. Limits of detection and quantification were 0.12-0.20 and 0.40-0.67 microm, respectively. This analytical method was applied in a preliminary study for the pronucleotide 2 quantification in cellular extract.     

Spectral and non-spectral interferences in inductively coupled plasma mass-spectrometry

Inductively coupled plasma mass spectrometry of environmental and biological samples is often hampered by spectral and non-spectral interferences. Spectral interferences, caused by the limited resolution of the quadrupole mass spectrometer, can be eliminated in a variety of ways. For their identification inspection of a signal versus carrier gas flowrate is useful. Anion exchange allows the removal of most S and Cl containing compounds, which are at the origin of the majority of spectral interferences. Matrix modification, for example the addition of ethanol and subsequent optimization of the gas flow rates in a number of cases enables the reduction of the interferences to insignificant values. Often a mathematical correction based on isotopic signal ratios can be applied. Non-spectral interferences can be divided in reversible, that is occurring while the sample is being measured, and irreversible matrix effects, that is clogging of the nebulizer and sampling orifices or deposition on the torch or in the ion lens stack. The errors associated with non-spectral interferences can be eliminated by appropriate calibration procedures, adapted sample preparation or limitation of the amount of sample delivered to nebulizer, plasma and sampling devices, for example by the application of flow injection. Applications of all the elimination procedures are described for the analysis of sea-water, estuarine water, soil and sewage extracts, percolate water, urine, serum and wine.     

Synthesis of 27-nor-25-oxocholest-5-en-3β-yl acetate and 27-nor-25-oxocholestanol from pregnenolone

Grignard-reaction of pregnenolone-3β-acetate with pentan-2-one ethylene ketal-5-magnesium bromide and subsequent dehydration yielded 27-nor-25-oxocholesta-5,20 (22)-dien-3β-yl acetate which was hydrogenated to 27-nor-25-oxocholest-5-en-3β-yl acetate and 27-nor-25-oxocholestan-3β-yl acetate.