Direct electrochemical synthesis and characterization of copper(II), iron(II) and iron(III) complexes with 1- and 2-substituted pyridines

Summary The electrochemical oxidation of anodic metals (iron and copper) in MeCN solutions of 2-pyridinone (HOPy), 1-hydroxy-2-pyridinethione (HPT), 2-pyridinemethanethiol-1-oxide (HPMTO) or its dimer 2,2-dithiodimethyldipyridine-1,1-dioxide (PMTO)₂, gave the simple complexes Fe(OPy)₂ · H₂O, Cu(OPy)₂ · 3H₂O, Fe(PT)₂ · 3H₂O, Fe(PT)₃, Cu(PT)₂, Fe(PMTO)₂·3H₂O and Cu(PMTO)₂·H₂O, respectively. When 1,10-phenanthroline (phen) was added to the electrolytic phase, only two mixed complexes were obtained: Cu(OPy)₂phen·3H₂O and Fe(PT)₂phen·2H₂O. The possible molecular structures of the complexes were studied on the basis of their i.r. spectra and magnetic properties.     

Determination of lead in wines by hydride generation atomic absorption spectrometry.

The optimization of lead hydride generation in aqueous ethanolic media and the influence on its generation of the wine components, both white and red, have been studied. These interferences were overcome by careful control of the parameters affecting hydride generation and the procedure was applied to the determination of Pb in wines. The method is fast, accurate and sensitive and can be used to quantify 24 ppb of Pb in wines.     

Peroxide derivatives of molybdenum(VI) in neutral and alkaline media

Summary The peroxidation of molybdenum(VI) was investigated in neutral and alkaline media. The stability constants of the peroxo complexes were determined by spectrophotometric measurement as (9.12±0.67)×10^–7, (2.68±0.17) ×10⁵, (1.26±0.06)×10⁶ and (1.58±0.02) for the 11, 21 (yellow), 31 and 41 (red) species. The diperoxomolybdate disproportionates into the tetraperoxo derivative when treated with alkali. Formation of the tetraperoxo complex was found to be pH dependent according to a curve, with maximum at pH 10. Acidification of tetraperoxomolybdate solution results in the regeneration of hydrogen peroxide and the diperoxo complex is reformed.     

Configuration and E/Z interconversion mechanism of O(S)-allyl-S(O)-methyl-N-(acridin-9-yl) iminothiocarbonate

The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S-allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the r(NOE). Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case-by-case basis.     

New cis-clerodane diterpenoids from Croton schiedeanus

The acid fraction of extracts from the aerial part of Croton schiedeanus afforded six cis-clerodane type diterpenoids. Two of them (1 and 4) are new natural compounds. Structural elucidation was achieved on the basis of their spectral data.     

Trapping Copper Phthalocyanine in a Silica Sono-Xerogel

A copper phthalocyanine (CuPc) has been encapsulated in silica. The trapping effects were studied comparing the UV-Vis absorption spectra of some CuPc solutions and composites prepared under different conditions. The trapped organic molecules’ stability was monitored during the gelation and drying processes. Leachability test have been carried out with the aim of checking the trapping efficiency. Hydrolysis water of pH=2 and a molar ratioR _w =6 mol acid H₂O/mol TMOS leads to a higher CuPc stacking angle homogeneity. The increase of Pc induces a narrower mesopore distribution and helps the stabilization of the composite.     

Covalently bonded platinum(II) complexes of alpha-amino acids and peptides as a potential tool for protein labeling

Arylplatinum(II) complexes have been covalently bonded to the N and C termini and to the alpha-carbon of various amino acid derivatives. These organometallic-functionalized amino acid compounds can be converted into the corresponding free amino acids under both basic and acidic conditions; this demonstrates the excellent stability properties of these biomolecules. Due to the NMR activity displayed by the 195Pt nucleus (natural abundance 33.8%, I = 1/2) these compounds are functional bio-markers. Furthermore, the ability of the arylplatinum functional group to bind SO2 gas, selectively and reversibly as indicated by changes in the spectroscopic properties (1H, 13C, 195Pt NMR and UV spectra) of these compounds, allows for the potential use of these complexes as in vitro biosensors.     

Determination of three anabolic compounds in calf urine by liquid chromatography with photodiode-array detection

A method for the determination of three anabolic hormones (diethylstilbestrol, dienestrol and trenbolone) in calf urine is described. After enzymatic hydrolysis, the samples were cleaned up by C18 solid-phase extraction. Drugs were extracted with hexane and analyzed by isocratic elution on a Discovery RP-Amide C16 5 microns column with photodiode-array detection at 240 and 347 nm. Both retention time and UV spectra were used for identification. Detection limits for the HPLC system were calculated to be 0.3 ng injected for all analytes in the standard mixture. However, for urine samples these limits increased because of the presence of unidentified matrix components. After extraction from urine, the limits of detection for the whole analytical procedure were 5 and 10 ng injected for trenbolone and stilbenes, respectively. The average recoveries of the hormones from spiked samples were in the range 53.1-56.7% with RSD between 11.3 and 14.5% for the whole procedure in the concentration range 25-2.5 ng ml-1.