Valency stabilization of polyvalent ions during gamma-irradiation of their aqueous solutions by sacrificial protection

The various aspects of valency stabilization of polyvalent ions during -radiolysis have been further investigated. Ce(IV) ions, which are normally reduced in their aqueous solution, were found to be stabilized for increasing periods of time when they were irradiated in the presence of increasing amounts of bromate ions. It was found that the addition of about fifteen times excess of bromate ions to a 10^–3 N Ce(IV) solution stabilized the cerium ions in the tetravalent state for about 120 hours during irradiation at a dose rate of 336 Gy/h. Increasing the amount of bromate used resulted in a subsequent increase in the protection time. It has been also noted that while bromate ions protected Ce(IV) in solution, the latter ions showed a clear protective effect on the bromate used, i.e., there is a mutual protective effect. The probable mechanisms, conditions and limitations of the protection process have been discussed. Based on the data obtained in the present work, it has been suggested that the protection of Ce(IV) ions by bromate ions in aqueous solutions during -radiolysis is very probably due to the preferential interaction of bromate with the reducing radiolysis products of water which are capable of reducing Ce(IV) to Ce(III).     

In vivo resolution of conflicting in vitro results: synthesis of biotin from dethiobiotin does not require pyridoxal phosphate

The source of the biotin sulfur atom remains a contested point in studies of biotin synthase (BioB) in vitro. Recent reports that BioB has an intrinsic pyridoxal phosphate (PLP)-dependent cysteine desulfurase activity were tested by depleting Escherichia coli cells of PLP. The BioB-dependent conversion of dethiobiotin to biotin proceeded in these cells irrespective of the presence or absence of PLP.     

Spectroscopic characterization of some metal complexes derived from 4-acetylpyridine nicotinoylhydrazone

Coordination compounds of Mn^II, Cu^II, Fe^III and Zn^II ions with 4-acetylpyridine nicotinoylhydrazone (4-APNH) were synthesized and characterized by elemental analyses, molar conductivity, magnetic moments, i.r., u.v./vis., m.s., ¹H-n.m.r. and thermal analyses. I.r. spectra show that the ligand can act either in the enol form as monovalent bidentate or in the keto form as neutral bidentate depending on the metal salt used. Octahedral structures are proposed for Fe complex and square – planar for the Cu complex, while tetrahedral structures were suggested for Zn and Mn complexes on the basis of magnetic and spectral evidences. Semi-empirical calculations ZINDO/1 have been used to study the molecular geometry and the harmonic vibrational spectra with the purpose to assist the experimental assignment of the complexes. In memory of the late Professor Dr. Abdel Hamid M. Shallaby 2/5/2006     

Novel spiro and fused heterocycles from the allylation of indigo

The allylation of indigo results in the one-step synthesis of two unique complex heterocyclic systems: a spiroindoline-pyridoindolone arising from the addition of three allyl moieties and a fused pyridoindolo-azepinoindolone generated from the addition and subsequent cyclisation of two allyl moieties. The structures of these novel heterocycles are assigned unambiguously using extensive NMR experiments and by X-ray crystallographic analysis. The distribution of the products is influenced by the use of thermal versus microwave heating.     

Determination of Dydrogesterone in Human Plasma by Tandem Mass Spectrometry: Application to Therapeutic Drug Monitoring of Dydrogesterone in Gynecological Disorders

A sensitive and specific tandem mass spectrometric (MS–MS) method was developed and validated for the determination of dydrogesterone (Duphaston^®), an orally active synthetic progestogen, in human plasma. Multiple reaction monitoring (MRM) scans at m/z 313.1 > 105.5 (dydrogesterone) and m/z 393 > 147 (dexamethasone, internal standard) were selected to determine dydrogesterone by the internal standard method. Linear correlations (r: ～0.99 ± 0.05) of the calibration curves were established over the concentration range 10–60 ng mL^?1 with a lower limit of quantification (LLQ) of 10 ng mL^?1 (RSD% 14.9 and %DEVs ?10.5 to +15.6). Solid-phase extraction (SPE) technique was used for extraction of dydrogesterone and internal standard from patient plasma samples using Oasis^® Max C18 cartridges. Ion suppression studies indicated negligible effects of plasma matrix on the mass ions detection of dydrogesterone and IS, when measured in MRM mode. Validation data showed that RSD% values were <22.0%, whereas %DEV values were in the range of ?20.2 to +13.3 for intra- and inter-day precision and accuracy, respectively. Analytical recoveries of dydrogesterone from supplemented plasma samples with the drug were in the range of 100.7–112%, indicating the efficiency of the SPE for separation of dydrogesterone from human plasma. Stability studies conducted at ?20 °C, showed that dydrogesterone was stable in plasma as indicated from the measured degradation kinetic parameters. The developed method was applied for monitoring plasma levels of dydrogesterone in 25 patients treated with Duphaston^® tablets at a dose of 10 mg three times daily. Mean plasma concentration of 16.1 ± 3.5 ng mL^?1 of dydrogesterone were measured at the steady state. The data suggest the utility of tandem mass method in therapeutic drug monitoring of plasma levels of dydrogesterone in gynecological disorders treated with Duphaston^® tablets.