New sensitive liquid chromatography method coupled with tandem mass spectrometric detection for the clinical analysis of vinorelbine and its metabolites in blood, plasma, urine and faeces

A new sensitive and specific liquid chromatographic method coupled with tandem mass spectrometric detection was set up and validated for the simultaneous quantitation of vinorelbine, its main metabolite, 4-O-deacetylvinorelbine and two other minor metabolites, 20'-hydroxyvinorelbine and vinorelbine 6'-oxide. All these compounds, including vinblastine (used as internal standard) were deproteinised from blood, plasma and faeces (only diluted in urine), analysed on a cyano column and detected on a Micromass Quattro II system in the positive ion mode after ionisation, using an electrospray ion source. Under tandem mass spectrometry conditions, the specific product ions led one to accurately quantify vinorelbine and its metabolites in all biological fluids. In whole blood, linearity was assessed up to 200 ng/ml for vinorelbine and up to 50 ng/ml for the metabolites. The limit of quantitation was validated at 250 pg/ml for both vinorelbine and 4-O-deacetylvinorelbine. In the other biological media, the linearity was assessed within a same range and the limit of quantitation was adjusted according to the expected concentrations of each compound. This method was initially developed in order to identify the metabolite structures and to elucidate the metabolic pathway of vinorelbine. Thanks to its high sensitivity, this method has enabled the quantitation of vinorelbine and all its metabolites in whole blood over 168 h (i.e., 4-5 elimination half lives) whilst the previous liquid chromatographic methods allowed their measurement for a maximum of 48-72 h. Therefore, using this method has improved the reliability of the pharmacokinetic data analysis of vinorelbine.     

Effect of the shear layer on the etching behavior of 6060 aluminum extrusion alloys

The occurrence of preferential grain etching (PGE) during alkaline etching of aluminum extrusion alloys from the 6XXX series is often linked to the presence of certain impurity elements such as zinc, causing an undesired etching appearance. In the presented work, an additional culprit in this context is identified, which has not been investigated yet. A clear relation between PGE and the presence of a subsurface shear layer is identified for extruded Al 6060 alloys containing 0.02 and 0.06 wt% Zn. This shear layer can be distinguished from the bulk of the metal by its difference in crystallographic texture as visualized by electron backscatter diffraction (EBSD). For the Zn enriched alloy, the <111>//ND grains are etched away faster than grains with other orientations, resulting in the grainy appearance typical for PGE. Independent of the Zn content in the alloy, once the shear layer is removed and <111>//ND grains are practically absent on the new surface, the depths variations caused by preferential etching disappear. Instead, the surface of the alloy is attacked uniformly by the caustic etch bath.     

THE EFFECT OF ACIDS ON THE INFRARED SPECTRA OF SCHIFF BASES—II. IMINES CONTAINING THE C=C-C=N AND C=C-C=C-C=N UNITS

Abstract— The Fourier-transform infrared spectra of chloroform-d solutions of conjugated imines CH₃CH=CHCH=NCH(CH₃)₂ and CH₃CH₂CH=CHCH=CHCH=NCH(CH₃)₂ and the related protonated species with HCl, HBr, HI, trichloro, dichloro, monobromo and monochloroacetic acids or propionic acid are presented. The effects of conjugation and protonation are examined. The results show that conjugation slightly increases the basicity of the Schiff bases. HCl, HBr and HI protonate the Schiff bases completely. The carboxylic acids protonate partially depending on their p K _a, values. When the Schiff base contains two (or more) C=C bonds conjugated with C=N, the main C=C stretching band undergoes a strong intensification showing that sizeable dipole moment variations occur along the conjugated chain.     

Control of the electrode temperature for electrochemical studies: A new approach illustrated on porous anodizing of aluminium

A new approach for studying the effect of temperature on electrochemical processes is presented in this paper. Using an in-house developed electrode holder, experiments are performed under conditions of applied and controlled electrode temperature. This new approach provides an improved temperature control during the experimental study and, additionally, allows distinguishing both the influences of the electrolyte and electrode temperatures. The advantages of the applied electrode temperature approach are illustrated by considering porous anodizing of aluminium. In a broad temperature range the electrochemical behaviour of the aluminium electrodes, recorded during the new and the conventional way of anodizing, are compared. Differences between the anodic potential evolutions in both approaches are observed, and are explained by a heat flux to the surroundings during the experiments at uncontrolled electrode temperature. These results illustrate the advantage of applying the electrode temperature. If the influence of temperature on a process is investigated by merely varying the electrolyte temperature, the electrode temperature is only indirectly influenced and can significantly differ from the electrolyte temperature. Therefore, when evaluating the influence of temperature on an electrochemical system the electrode temperature should be considered, and preferentially also controlled.     

Pr?parative Trennung von biologisch aktiven Ribonucleins?uren durch HPLC

Ohne Zusammenfassung

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Preparative separation of biologically active ribonucleic acids by HPLC

     

Ionic concentration effects on reverse micelle size and stability: implications for the synthesis of nanoparticles

We present a systematic investigation and analysis of the structure and stability of reverse micelle systems with the addition of NH(4)OH, ZrOCl(2), and Al(NO(3))(3) salts. We demonstrate that the reverse micelle size decreases with increasing salt additions until one reaches a critical concentration, which characterizes the onset of system destabilization. The concept of an electrical double layer, as it applies to reverse micelles, is considered for explaining features of destabilization, including the initial decrease in reverse micelle size, the destabilization concentration, and the effect of cation valence. We propose that the reduction in size prior to instability is caused by compression of the reverse micelle electrical double layers, as higher concentrations of salts are present. The reduced thickness of the electrical double layers allows the decaying potentials to move into closer proximity to each other before generating enough repulsion to balance the forces for reverse micelle formation and form a new equilibrium average reverse micelle size. The point of reverse micelle instability has been related to the formation of a two-phase system as a result of the inability to further compress the salt co-ions in the core of the reverse micelles, which would cause an excessive repulsive force between the overlapping potentials. We have extracted a critical potential of -89 nV between the two overlapping potentials for the AOT/water/isooctane (ω(0) = 10) systems studied. All these effects have important implications for the preparation of nanopowders by reverse micelle synthesis. If the reverse micelles are unstable before the precipitates are formed, then the advantage of reverse micelle synthesis is immediately lost.