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31.
The adsorption, diffusion and desorption of chlorine on and from stoichiometric, reduced and partially reduced (defective) rutile TiO2{110} are investigated using ab initio density functional theory (DFT) calculations. Theoretical results are compared with experimental investigations, and microkinetic simulations based on DFT values are then used to verify the diffusion mechanisms assumed in the experimental investigations. 相似文献
32.
33.
Berhan Teclé Kaniz F. Siddiqui Christopher Ceccarelli John P. Oliver 《Journal of organometallic chemistry》1983,255(1):11-15
The structure of di-trans-β-styrylmercury has been determined by single crystal X-ray methods from counter data. The compound crystallizes in the orthorhombic space group Pbcn with unit cell dimensions a 15.413(6), b 11.161(9), c 7.668(5) Å, V 1319(1) Å3, Dcalc 2.049 g/cm3, and Z = 4. The crystal was solved by conventional heavy atom techniques. The crystal consists of individual molecular units with the mercury atom located on a two fold axis of symmetry. The CHgC fragment is nearly linear with an angle of 178°. The β-styryl groups are oriented so that a dihedral angle of 66.8° is formed between the planes defined by HgC(1)C(2) and HgC(1)′C(2)′ fragments. The HgC bond distance is 2.07(4) Å. 相似文献
34.
Comparison of different extraction techniques for the determination of polychlorinated organic compounds in sediment 总被引:2,自引:0,他引:2
Martens D Gfrerer M Wenzl T Zhang A Gawlik BM Schramm KW Lankmayr E Kettrup A 《Analytical and bioanalytical chemistry》2002,372(4):562-568
The performance of various enhanced extraction techniques, such as accelerated solvent extraction, microwave-assisted extraction, Soxhlet extraction, ultrasonic extraction and fluidized-bed extraction for the determination of polychlorinated organic compounds in dry sediment was investigated in two laboratories. The results of the two laboratories were in good agreement. The extraction yields from the batch extraction methods were lower than those from the dynamic techniques. Accelerated solvent extraction, especially, exhibited higher extraction efficiency than the standard procedure, Soxhlet extraction, whereas the results of fluidized-bed extraction were comparable. 相似文献
35.
The electro-oxidation of CO on model platinum-tin alloy catalysts has been studied by ex-situ electrochemical measurements following the preparation of the Pt(111)/Sn(2x2) and Pt(111)/Sn(radical3 x radical3)R30 degrees surfaces. A surface redox couple, which is associated with the adsorption/desorption of hydroxide on the Sn sites, is observed at 0.28 V(RHE)/0.15 V(RHE) in H(2)SO(4) electrolyte on both surfaces. Evidence that it is associated with the adsorption of OH comes from ex-situ photoemission measurements, which indicate that the Sn atoms are in a metallic state at potentials below 0.15 V(RHE) and an oxidized state at potentials above 0.28 V(RHE). Specific adsorption of sulfate anions is not associated with the surface process since there is no evidence from photoemission of sulfate adsorption, and the same surface couple is observed in the HClO(4) electrolyte. CO is adsorbed from solution at 300 K, with saturation coverages of 0.37 +/- 0.05 and 0.2 +/- 0.05 ML, respectively. The adsorbed CO is oxidatively stripped at the potential coincident with the adsorption of hydroxide on the tin sites, viz., 0.28 V(RHE). This strong promotional effect is unambiguously associated with the bifunctional mechanism. The Sn-induced activation of water, and promotion of CO electro-oxidation, is sustained as long as the alloy structure remains intact, in the potential range below 0.5 V(RHE). The results are discussed in the light of the requirements for CO-tolerant platinum-based electrodes in hydrogen fuel cell anode catalysts and catalysts for direct methanol electro-oxidation. 相似文献
36.
Van Der Eycken E Appukkuttan P De Borggraeve W Dehaen W Dallinger D Kappe CO 《The Journal of organic chemistry》2002,67(22):7904-7907
Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed. 相似文献
37.
The electron capture negative ion (ECNI) mass spectra of two complex mixtures of polychlorinated decanes (PCDe) and polychlorinated
dodecanes (PCDo) are presented. The number of isomers in these mixtures is still high but is drastically reduced in comparison
to technical products of chlorinated paraffins (CP), due to their fixed chain length. As a result, the mass spectra are simplified
and less complex. Different modes of negative ion formation were observed in the spectra of the PCDe and PCDo. [M+Cl]– adduct ions were the most abundant ions in the spectra of lower chlorinated molecules. Higher chlorinated isomers formed
prominently [M-Cl]– and [M-HCl]– fragments besides [M+Cl]–. Possible consequences for the determination of chlorinated paraffins by ECNI-MS that result from the variation in ion formation
are addressed.
Received: 18 August 1997 / Revised: 26 January 1998 / Accepted: 31 January 1998 相似文献
38.
Chiral carbenium ions can be attacked by arene nucleophiles with high facial diastereoselectivity (dr >/= 94/6). Benzylic cations, such as 2, were generated under acidic conditions and reacted with arenes in intra- and intermolecular Friedel-Crafts alkylation reaction. The depicted reaction 1 --> 3 represents one example for the unprecedented, highly diastereoselective intermolecular Friedel-Crafts alkylation reactions which were observed in this study. 相似文献
39.
Kratzsch C Tenberken O Peters FT Weber AA Kraemer T Maurer HH 《Journal of mass spectrometry : JMS》2004,39(8):856-872
A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (LC/APCI-MS) is presented for fast and reliable screening and identification and also for precise and sensitive quantification in plasma of the 23 benzodiazepines alprazolam, bromazepam, brotizolam, camazepam, chlordiazepoxide, clobazam, clonazepam, diazepam, flunitrazepam, flurazepam, desalkylflurazepam, lorazepam, lormetazepam, medazepam, metaclazepam, midazolam, nitrazepam, nordazepam, oxazepam, prazepam, temazepam and tetrazepam, triazolam, their antagonist flumazenil and the benzodiazepine BZ1 (omega 1) receptor agonists zaleplone, zolpidem and zopiclone. It allows confirmation of the diagnosis of an overdose situation and monitoring of psychiatric patients' compliance. The analytes were isolated from plasma using liquid-liquid extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' LC/MS library, the analytes were quantified in the selected-ion monitoring mode. The quantification assay was fully validated. It was found to be selective proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes, except bromazepam. The corresponding reference levels the assay's accuracy and precision data for all studied substances are listed. The accuracy and precision data were within the required limits with the exception of those for bromazepam. The analytes were stable in frozen plasma for at least 1 month. The validated assay was successfully applied to several authentic plasma samples from patients treated or intoxicated with various benzodiazepines or with zaleplone, zolpidem or zopiclone. It has proven to be appropriate for the isolation, separation, screening, identification and quantification of the drugs mentioned above in plasma for clinical toxicology, e.g. in cases of poisoning, and forensic toxicology, e.g. in cases of driving under the influence of drugs. 相似文献
40.
Elke Barsties Stefan Schaible Marc-Heinrich Prosenc Ursula Rief Werner Rll Oliver Weyand Birgit Dorer Hans-Herbert Brintzinger 《Journal of organometallic chemistry》1996,520(1-2):63-68
Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH3)2N-C9H6)2ZrCl2, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2, were prepared by reaction of the corresponding ligand lithium salts with ZrCl4 in toluene. Diffractometric structure determinations reveal C2-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2 catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me2Si-bridged bis(indenyl)ZrCl2 complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species. 相似文献