The mechanism of the copper-mediated disproportionation of aromatic imine disulfides to benzothiazoles in the gas phase is investigated by experimental and theoretical methods. Application of infrared multiphoton dissociation and hydrogen/deuterium exchange experiments combined with density functional theory (DFT) calculations of the relevant molecular structures and the associated infrared spectra allows the identification of the observed ionic intermediates. The theoretical investigation of the possible reaction pathways supported by collision-induced dissociation experiments provides a consistent mechanistic picture of the reaction catalyzed by a single copper(I) ion. Activation of the substrate proceeds via homolytic sulfur-sulfur bond cleavage, yielding metal complexes in the formal +3 oxidation state; carbon-sulfur coupling and hydrogen-atom transfer complete the transformation to the products. Exploratory studies demonstrate that in the gas phase, the disproportionation of the imine disulfide can also be mediated by other metal ions via different either homo- or heterolytic mechanisms without involving high-valent intermediates. 相似文献
Zusammenfassung Die Jodidoxydation durch Cu(II) wird in Anwesenheit von Ammoniak, Natriumtartrat, citrat oder -oxalat infolge Komplexbildung verhindert. Daher kann man z. B. Quecksüber(II) in Anwesenheit der genannten Komplexbildner mit Kaliumjodid maskieren und Kupfer(II) durch direkte Titration mit ÄDTA gegen Murexid, Brenzcatechinviolett, Chromazurol S, PAN oder PAR als Indikator bestimmen.
Masking with potassium iodide in direct titrations of copper(II) with ethylenediamine tetraacetic acid
Summary The formation of a complex prevents the iodide oxidation by Cu(II) in the presence of ammonia, sodium tartrate, citrate, or oxalate. Hence mercury(II) for instance, can be masked against potassium iodide in the presence of these complex formers, and Cu(II) can be determined by direct titration with EDTA in the presence of murexide, pyrocatechol violet, chromazurol, PAN or PAR as indicator.
Zusammenfassung Eine Studie über die Deblockierung von Metallindicatoren bei chelometrischen Titrationen in Gegenwart von organischen Lösungsmitteln wurde unternommen. Als Beispiele dienten die Bestimmungen von Kobalt, Eisen(III), Kupfer, Mckel und Aluminium in Gegenwart der in der Tabelle angegebenen organischen Lösungsmittel. Dazu versetzte man mit überschüssiger ÄDTA-Lösung und titrierte gegen Eriochromschwarz T als Indicator zurück. Eine Erklärung des Einflusses der organischen Lösungsmittel auf den Titrationsverlauf wurde versucht.
Summary The deblocking of metal indicators in chelometric titrations in the presence of organic solvents has been studied. As examples the titrations of cobalt, iron(III), copper, nickel and aluminium have been performed in the presence of the organic solvents mentioned in the table. The sample solution was mixed with an excess of EDTA solution and backtitrated with Eriochrome Black T as an indicator. It has been tried to elucidate the effect of the organic solvents on the titration.
Mein ganz besonderer Dank gilt an dieser Stelle Herrn Prof. Dr. L.Erdey, nicht nur für sein Interesse an dieser Arbeit und seine fördernden Ratschläge, sondern auch für freundliche Aufnahme an seinem Institut.Für wertvolle Hilfe danke ich den Herren Dr. Dipl.-Ing.Gy. Rády, Dr. Dipl.-Ing. F.Szabadváry und Dipl.-Ing. O.Weber. 相似文献
The adsorption of 1-octanol at the free water surface has been investigated by Monte Carlo computer simulation. Six different systems, built up by an aqueous and a vapor phase, the latter also containing various number of octanol molecules, have been simulated. The number of the octanol molecules has been chosen in such a way that the octanol surface density varies in a broad range, between 0.27 and 7.83 micromol/m(2) in the six systems simulated. For reference, the interfacial system containing bulk liquid octanol in the apolar phase has also been simulated. The results have shown that the formation of hydrogen bonds between the interfacial water and adsorbed octanol molecules is of key importance in determining the properties of the adsorbed layer. At low octanol surface concentration values all the octanol molecules are strongly (i.e., by hydrogen bonds) bound to the aqueous phase, whereas their interaction with each other is negligibly small. Hence, they are preferentially oriented in such a way that their own binding energy (and thus their own free energy) is minimized. In this preferred orientation the O-H bond of the octanol molecule points flatly toward the aqueous phase, declining by about 30 degrees from the interfacial plane, irrespectively from whether the octanol molecule is the H-donor or the H-acceptor partner in the hydrogen bond. Hence, in its preferred orientation the octanol molecule can form at least two low energy hydrogen bonds with water: one as a H-donor and another one as a H-acceptor. Moreover, the preferred orientation of the hydrogen bonded water partners is close to one of the two preferred interfacial water alignments, in which the plane of the water molecule is parallel with the interface. When increasing the octanol surface density, the water surface gets saturated with hydrogen bonded octanols, and hence any further octanol molecule can just simply condense to the layer of the adsorbed octanols. The surface density value at which this saturation occurs is estimated to be about 1.7 micromol/m(2). Above this surface density value the hydrogen bonded octanols and their water partners are oriented in such a way that the number of the water-octanol hydrogen bonds is maximized. Hence, the preferred alignment of the O...O axes of these hydrogen bonds is perpendicular to the interface. This orientation is far from the optimal alignment of the individual octanol molecules, which is also reflected in the observed fact that, unlike in the case of many other adsorbents, the average molecular binding energy of the adsorbed octanol molecules increases (i.e., becomes less negative) with increasing octanol surface density. 相似文献
Summary The fast flow technique with OH resonance fluorescence detection has been applied at T = 298 ± 2 K to study the kinetics of the overall reaction: H + CH3C(O)Cl → products (1) A rate constant value of k1 = (1.02 ± 0.12) x 1010 cm3 mol-1 s-1 has been determined which is the first direct kinetic parameter reported for reaction (1) in the literature (the error given
refers to 2σ accuracy). 相似文献
Five chiral -D-glucose-based monoaza-15-crown-5 ethers with phosphinoxidoalkyl side chains of one to five carbon atoms (5a–e)have been synthesised. The cation binding ability of the new lariat ethers was evaluated bythe picrate extraction method. The substituents at the nitrogen atom were not a major influenceon the cation extraction ability of the azacrown ether; the compounds showed, however, a significant asymmetric induction as phase transfer catalysts in the Michael addition of2-nitropropane to chalcone (95% ee). 相似文献
A novel capillary zone electrophoresis method was developed to investigate the glycoform heterogeneity of human serum α1-acid glycoprotein (AGP). The simultaneous application of a dimethyl polysiloxane coated capillary and oligoamine additives, particularly spermidine resulted in a more detailed separation of AGP glycoforms than reported previously. The relative distribution of AGP glycoforms in CZE was determined by baseline integration of peak areas and verified by peak-fitting analysis. Providing high purity of AGP samples suitable for CZE a schedule of isolation and purification steps including sample preparation and an improved technique of ion exchange chromatography was applied. Based on data obtained by CZE and on the serum AGP levels measured the serum concentrations of AGP glycoforms were calculated in cancer patients with Hodgkin and non-Hodgkin lymphoma, ovary carcinoma and melanoma compared to healthy donors. Results presented here demonstrated a significant increase in the serum concentration of the more acidic AGP fractions also indicating the overproduction of these glycoforms in cancer. In conclusion, our observations may raise the clinical diagnostic relevance of changes in the molecular heterogeneity of AGP detected by CZE in the various forms of malignant diseases.
A new efficient interval partitioning approach to solve constrained global optimization problems is proposed. This involves
a new parallel subdivision direction selection method as well as an adaptive tree search. The latter explores nodes (intervals
in variable domains) using a restricted hybrid depth-first and best-first branching strategy. This hybrid approach is also
used for activating local search to identify feasible stationary points. The new tree search management technique results
in improved performance across standard solution and computational indicators when compared to previously proposed techniques.
On the other hand, the new parallel subdivision direction selection rule detects infeasible and suboptimal boxes earlier than
existing rules, and this contributes to performance by enabling earlier reliable deletion of such subintervals from the search
space. 相似文献