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A Mechanistic Study on the Oxidative Degradation of Dibenzazepine Derivatives by Manganese(III) Complexes in Acidic Sulfate Media 下载免费PDF全文
The oxidative degradation of tricyclic antidepressants (TCA) was studied in the presence of a large excess of the oxidizing agent manganese(III) and its reduced form manganese(II) sulfate in acidic media. The products were detected and identified using UV–vis, ESI‐MS, IR, and EPR methods. The mechanism of the reaction was studied for the following two classes of TCA: 10,11‐dihydro‐5H‐dibenz[b, f]azepines and dibenz[b, f]azepines. The oxidative degradation between dibenz[b, f]azepines and the manganese(III) ions resulted in the formation of substituted acridine with the same substituent as in the origin dibenz[b, f]azepine derivative. The pseudo–first‐order rate constants (kobs) were determined for the degradation process. The dependences of the observed rate constants on the [MnIII] with a zero intercept were linear. The reaction between 10,11‐dihydro‐5H‐dibenz[b, f]azepines, and the manganese(III) sulfate ion resulted in oxidative dehydrogenation, which proceeded via the formation of the following two intermediates: a free organic radical and a dimer. Further oxidation of the second intermediate led to a positively charged radical dimer as the single final product. Linear dependences of the pseudo–first‐order rate constants (kobs) on the [MnIII] with a zero intercept were established for the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines. The observed rate constants were dependent on the [H+] and independent of the [TCA] within the excess concentration range of the manganese(III) complexes used in the isolation method. The radical product of the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines was not stable in the aqueous solution and was subsequently transformed to a nonradical dimer in the next slower step. The observed rate constants were independent of the [MnIII], independent of the [H+] and increased slightly with increasing TCA concentrations when TCA was used in excess. The mechanistic consequences of all of these results are discussed. 相似文献
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M. A. Augustyniak-Jabłokow K. Łukaszewicz A. Pietraszko V. E. Petrashen Yu. V. Yablokov 《Physics of the Solid State》2002,44(8):1480-1483
The EPR spectra evolution of Cs2Zn1?x Cux(ZrF6)2 · 6H2O (x=0.01, 0.6, 0.8, and 1.0) in the temperature range 4.2–330 K and the x-ray structure analysis of the compound with x=1.0 in the range 150–327 K show that the Jahn-Teller (JT) complex Cu(H2O)6 coordination sphere undergoes a plastic deformation. The observed effect is due to the combined influence of small lattice strains existing in the paraphase and a new one appearing as a result of a ferroelastic phase transition and increasing with decreasing temperature below T c . It is proved that both cooperative interactions between JT complexes and ferroelastic strain stabilize a certain JT configuration. The problem of instability of a JT configuration compressed at T ~ 265 K is discussed. 相似文献
4.
Teresa uczak Radosaw Pankiewicz Bogusawa ska Grzegorz Schroeder Maria Betowska-Brzezinska Bogumil Brzezinski 《Journal of Molecular Structure》2006,800(1-3):140-145
Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li+ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods. 相似文献
5.
Jacek Doskocz Jadwiga Sołoducho Joanna Cabaj Mieczysław Łapkowski Sylwia Golba Krystyna Palewska 《Electroanalysis》2007,19(13):1394-1401
A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique. 相似文献
6.
J. Łukasik G. Auger M. L. Begemann-Blaich N. Bellaize R. Bittiger F. Bocage B. Borderie R. Bougault B. Bouriquet J. L. Charvet A. Chbihi R. Dayras D. Durand J. D. Frankland E. Galichet D. Gourio D. Guinet S. Hudan P. Lautesse F. Lavaud A. Le Fèvre R. Legrain O. Lopez U. Lynen W. F. J. Müller L. Nalpas H. Orth E. Plagnol E. Rosato A. Saija C. Schwarz C. Sfienti B. Tamain W. Trautmann A. Trzciński K. Turzó E. Vient M. Vigilante C. Volant B. Zwiegliński 《Acta Physica Hungarica A》2006,25(2-4):229-239
Directed and elliptic flow for the 197Au+197Au system at incident energies between 40 and 150 MeV per nucleon has been measured using the INDRA 4π multi-detector. For semi-central collisions, the excitation function of elliptic flow shows a transition from in-plane to out-of-plane emission at around 100 MeV per nucleon. The directed flow changes sign at a bombarding energy between 50 and 60 MeV per nucleon and remains negative at lower energies. Molecular dynamics calculations (CHIMERA) indicate sensitivity of the global squeeze-out transition on the σ NN and demonstrate the importance of angular momentum conservation in transport codes at low energies. 相似文献
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In this Note we first introduce the concept of pullback asymptotic compactness. Next, we establish a result ensuring the existence of a pullback attractor for a non-autonomous dynamical system under the general assumptions of pullback asymptotic compactness and the existence of a pullback absorbing family of sets. Finally, we prove the existence of a pullback attractor for a non-autonomous 2D Navier–Stokes model in an unbounded domain, a case in which the theory of uniform attractors does not work since the non-autonomous term is quite general. To cite this article: T. Caraballo et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006). 相似文献
10.
A. Deptuła T. Olczak W. Łada B. Sartowska A.G. Chmielewski C. Alvani P.L. Carconi A. Di Bartolomeo F. Pierdominici S. Casadio 《Journal of Sol-Gel Science and Technology》2003,26(1-3):207-212
Microspheres of Li2TiO3 were fabricated by a classical, inorganic sol-gel process from commercially available TiCl4. Elaborated process consists of the following main steps: (1) dissolving of TiCl4 in concentrated aqueous HCl and addition of LiOH; (2) formation of sol emulsion in 2-ethylhexanol-1 containing the surfactant SPAN-80 (EH); (3) gelation of emulsion drops by extraction of water with partially dehydrated EH; (4) impregnation of gel to Li:Ti molar ratio MR = 2; (5) thermal treatment at 1200°C in order to receive chloride free product. This temperature can be significantly lowered (to 750°C) by dechlorination starting solution TiCl4 by chemical treatment of the with nitric acid to form of nitrate-stabilized titania sols. Tritium release from sol-gel made Li2TiO3 microspheres were found very close to that observed for other traditional materials, however for the first sample process starts slightly earlier. 相似文献