Recherches en série triazepine-1,2,4: 1 - détermination de la structure de la triazolotriazépinone obtenue par action de l'acétylacétate d'éthyle sur le diamino-3,4 triazole-1,2,4

The condensation of 3,4-diamino 1,2,4-triazole with ethyl aceloacelate gave 6-methyl-8,9-dihydro(7H)-s-triazolo[4,3-b]-1,2,4-triazepin-8-one ( 2 ); 2 has been caracterized by nmr spectroscopy and by comparison with its methylated derivative prepared in an unambigous manner.     

Self-association of daunomycin antibiotic in various buffer solutions

The self-association of an antitumor antibiotic, daunomycin (DAU), in various buffer solutions, including water-salt solutions, phosphate buffer, HEPES, and TRIS, was studied by 1D and 2D ¹H NMR spectroscopy at 500 MHz. The two-dimensional NOESY spectra and the concentration and temperature dependences of the chemical shifts of antibiotic protons in the solvents studied showed that the self-association parameters of DAU were independent of the type of buffer solutions. The most probable two spatial structures of the dimer of DAU in solution were constructed by the method of molecular mechanics. The mutual orientation of the chromophores was parallel in one structure and antiparallel in the other.     

Glass forming ability and thermal stability in the system ZrF46BaF26PrF3

New glasses have been synthesized in the system ZrF₄6BaF₂6PrF₃. Glasses were prepared by conventional fusion method and the vitreous domain was established. For vitreous samples the thermal stability parameters were determined, so that the best compositions could be selected according to a compromise between high glass forming ability and thermal stability vs. crystallization.     

Infrared laser ablation study of pressed soil pellets with inductively coupled plasma atomic emission spectrometry

Potential of infrared laser ablation (LA) coupled with ICP-AES as a technique suitable for the determination of trace elements (Zn, Cu, Ni, Cr, and V) in agricultural soils was studied. Operating parameters such as laser beam energy, laser beam focusing with respect to the sample surface, and velocity of the sample translation in the plane perpendicular to the laser beam were optimized. Soil samples were mixed with powdered Ag as a binder, and an internal standard (GeO(2)), and pressed into pellets. Calibration samples were prepared by adding known amounts of oxides of elements of interest into soils of known elemental composition and then processed in the same way as the analyzed samples. Calibration curves were found to be linear at least up to several hundreds of mg kg(-1) for the elements of interest. The elemental contents obtained by using LA-ICP-AES were compared with those obtained by analysis using wet chemistry followed by ICP-AES with pneumatic nebulization (PN). The results were in good agreement. Accuracy was also tested using certified reference soils with a bias not exceeding 10% relative.     

Multibiosensor based on enzyme inhibition analysis for determination of different toxic substances

An original concept of an enzyme multibiosensor for determination of toxic substances based on enzyme inhibition analysis has been proposed and its main performances have been analysed. For the development of this multibiosensor, two types of transducers such as potentiometric pH-sensitive field-effect transistors and conductometric thin-films interdigitated electrodes, and three enzymes, namely urease, acetylcholinesterase and butyrylcholinesterase have been used. The experimental data have been treated by multivariate correspondence analysis. A complete procedure for a simultaneous determination of some heavy metal ions and pesticides has been proposed and its advantages have been discussed.     

Experimental and theoretical study of vibrational spectra and structure of dihalogermylene and dihalostannylene complexes with 1,4-dioxane and triphenylphosphine

Vibrational (Raman and IR) spectra of the 1:1 complexes of dihalogermylene and dihalostannylene with 1,4-dioxane and PPh₃ have been reported, the structures of the complexes Cl₂Ge·C₄H₈O₂ and Cl₂Ge·PPh₃ updated using high-resolution X-ray method. Quantum-chemistry calculations of the geometry and normal mode frequencies and eigenvectors were carried out for some of the complexes. The results show that in the structure of the polymeric solid complexes of X₂M with 1,4-dioxane, intermolecular coordination XM plays a prominent role, whereas the corresponding complexes with PPh₃ are monomeric. In the vibrational spectra of all the complexes, an inversion of symmetric and antisymmetric stretching νXM (X=Cl, Br; M=Ge, Sn) frequencies, found for ‘free’ X₂M^II particles, still persists, suggesting that the X₂M moieties preserve their specifity as carbene analogues also in the complexes.     

Separation of dideoxyribonucleosides in trace amounts by automated liquid chromatography and capillary electrophoresis.

No satisfactory high-performance liquid chromatographic (HPLC) method is currently available for the separation of the major dideoxyribonucleosides (ddNs) and their derivatives. A method involving HPLC has been developed for the separation of five major ddNs [ddA, ddC, ddI, azT and 2',3'-dideoxy-2',3'-didehydrothymidine (d4T)]. Elution of the common and modified components of DNA was also examined under the selected separation conditions of HPLC. The elution characteristics of these compounds were studied using serum plasma samples spiked with ddN derivatives. In addition, capillary electrophoresis (CE) was investigated for the separation of ddNs and their derivatives. Picomolar amounts of the five major ddNs and the metabolic product of azT [5'-O-glucuronide-3'-azido-3'-deoxythymidine (Glo-azT)] were satisfactorily resolved in 10 min by using a modification of CE. The spectral properties of the ddNs were characterized under different pH conditions and compared with those of their parent deoxyribonucleosides (dNs) because these compounds are commonly measured in HPLC by their spectral properties. The spectra of ddC and ddT derivatives resemble very closely those of dC and dT, but those of ddA and ddI differ to some extent from their parent dNs. The HPLC method was extensively examined for satisfactory resolutions of these compounds. For example, an isocratic elution method, although simple, failed to resolve these compounds and ion-pair chromatography did not offer any advantage. Gradient elution involving buffered solutions and increasing amounts of an organic modifier yielded satisfactory results. Methanol appeared to be the organic modifier of choice. A reversed-phase matrix with smaller than octadecyl alkyl chains did not produce the necessary interactions. Uniform spherical beads of smaller diameter produced superior resolutions. The separation of these compounds on three commercially available columns is discussed. The separation of human plasma samples spiked with dideoxynucleoside derivatives by HPLC was accomplished in ca. 16 min. The presence of the dNs did not interfere in their separations.     

Automated measurement of dye coverage in photographic negatives by flow-injection analysis

A system was designed to automate the determination of three image dyes in an instant photographic material. The method involves extracting negative samples with dimethylsulfoxide and filtering the extract, followed by quantitating the dye coverage (dye per unit area of negative) through a spectrophotometric flow-injection procedure. Significant spectral overlap exists among the dyes, and as a result calculation of coverage requires solving three simultaneous equations. A microcomputer and data acquisition system were employed for controlling the detector and flow-injection system, acquiring and integrating the detector response, calculating coverage, producing and displaying control charts, and automatically transferring results to a VAX based corporate database. In addition to automating sample preparation and measurement steps as much as possible, the goal of this project was to automate the data manipulation and transfer steps.