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981.
Raif Kurtaran Cengiz Arici Kaan C. Emregül Diner Ülkü Orhan Atakol Mustafa Tatekin 《无机化学与普通化学杂志》2003,629(9):1617-1621
A homo‐dinuclear NiII complex was prepared from 2, 6‐bis(3, 5‐dimethylpyrazolyl)pyridine (Me4‐bpp) and azide ions in nonaqueous media. It was characterized by single crystal X‐ray structural analysis, IR spectroscopy, and elemental analysis. In addition, the electrochemical properties of the compound were determined with cyclic voltammetry in DMF. The title compound crystallizes in the P21/n monoclinic space group, with unit cell parameters a = 8.978(1), b = 12.459(1), c = 17.764(1) Å, ß =100.603(3)°, V = 1953.0(3) Å3, Z = 2. The Ni2+ ion has a distorted octahedral environment involving three nitrogen atoms of the Me4‐bpp ligand, two nitrogen atoms from the bridged azide group, and one nitrogen atom from the terminal azide group. The Ni···Ni distance is 3.273(5) Å. 相似文献
982.
In this study, a syringe was filled with silica gel loaded with 3-aminopropyltriethoxysilane, for the separation and preconcentration of copper, cadmium and chromium prior to their determination by graphite furnace atomic absorption spectrometry (GFAAS) in seawater. For this purpose, a syringe was filled with 0.5 g of modified silica gel and the sample solution was drawn into the syringe and ejected back again. The analyte elements were quantitatively retained at pH 5. Then, the elements sorbed by the silica gel were eluted with 2.0 M of HCl and determined by GFAAS. At optimum conditions, the recovery of Cu, Cd and Cr were 96-98%. Detection limits (3delta) were 6.6, 7.5 and 6.0 micro g L(-1) for Cu, Cd and Cr, respectively. The elements could be concentrated by drawing and discharging several portions of sample successively but eluting only once. Cu, Cd and Cr added to a seawater sample were quantitatively recovered (>95%) in the range of the 95% confidence level. The method proposed in this paper was compared with a column technique. Optimum experimental conditions, reproducibility, precision and recoveries of both techniques are the same, but the syringe technique is much faster, easier and more practical than the column technique. It is a portable system and allows one to make the sorption process in the source of sample. In addition, the risk of contamination is less than in the column technique. 相似文献
983.
The adsorption/desorption process of borate was studied at Pt(111) in acidic solution by cyclic voltammetry. A so-called butterfly
wave in the cyclic voltammogram of Pt(111) in HClO4 shifted to negative direction upon the addition of boric acid with the disappearance of its sharp spikes. The shift in potential
was found to be −57 mV with a tenfold increase of boric acid concentration. This illustrates that this anomalous wave is due
to borate adsorption/desorption by a one-electron transfer process. The borate adsorption/desorption wave was observed to
shift by −63 mV/pH. At pH>3, the anomalous wave splits forming two separate waves, depending on the pH and the scan rate.
The appearance of two waves is assigned to the change in the adsorption mode of borate or the participation of OH in the adsorption
process. 相似文献
984.
Vijayasarathi Nagarajan Barbara Müller Oksana Storcheva Klaus Köhler Andreas Pöppl 《Research on Chemical Intermediates》2007,33(8):705-724
Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)2) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin
echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data
of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental
and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)2 and chloroform interacts via hydrogen bonding to oxygens of the acac ligands. 相似文献
985.
We have used the oscillating peroxidase-oxidase (PO) reaction as a model system to study how oscillatory dynamics may affect the influence of toxic reaction intermediates on enzyme stability. In the peroxidase-oxidase reaction reactive intermediates, such as hydrogen peroxide, superoxide, and hydroxyl radical are formed. Such intermediates inactivate many cellular macromolecules such as proteins and nucleic acids. These reaction intermediates also react with peroxidase itself to form an inactive enzyme. The fact that the PO reaction shows bistability between an oscillatory and a steady state gives us a unique possibility to compare such inactivation when the system is in one of these two states. We show that inactivation of peroxidase is slower when the system is in an oscillatory state, and using numerical simulations we provide evidence that oscillatory dynamics lower the average concentration of the reactive intermediates. 相似文献
986.
Mahata PK Venkatesh C Syam Kumar UK Ila H Junjappa H 《The Journal of organic chemistry》2003,68(10):3966-3975
A simple, highly efficient, and regioselective synthesis of functionalized quinolines through Vilsmeier cyclization of a variety of alpha-oxoketene-N,S-anilinoacetals has been reported. The cyclization is found to be facile with N,S-acetals bearing strongly activating groups on aniline, whereas yields of quinolines are moderate in other cases. The reaction could also be extended for the synthesis of substituted tricyclic benzo[h]quinoline, pyrido[2,3-h]quinoline, 4,7-diphenylphenanthroline, and tetracyclic quino[8,7-h]quinoline by performing a Vilsmeier reaction on N,S-acetals derived from 1-naphthylamine, m-phenylenediamine, o-phenylenediamine, and 1,5-diaminonaphthalene, respectively. A few of the newly synthesized quinolines are subjected to further transformation to afford 2-unsubstituted (Raney-Ni/Ethanol), quinoline-5,8-quinone (NBS/H(2)SO(4)), or 2-alkyl/aryl aminoquinolines through sequential m-CPBA oxidation to the corresponding (2-methylsulfonyl)quinoline followed by replacement with appropriate amines. Similarly, cycloannulation of a few 2-methylthio-3-benzoylquinolines with hydrazine hydrate under microwave irradiation afforded the corresponding substituted and fused pyrazolo[3,4-b]quinolines in excellent yields, whereas TBTH/AIBN-mediated cyclization of the corresponding 3-(2-bromobenzoyl)-2-methylthioquinolines yielded the corresponding benzothiopyrano-fused quinolines through radical translocation. 相似文献
987.
Complexes of FeI2 and FeI3 with Tetramethylurea [FeI2(OC(NMe2)2)2] ( 1 , [Fe2I4(OC(NMe2)2)2] ( 2 ), and [FeI3(OC(NMe2)2] ( 3 ) were prepared by the reaction of FeI2 and FeI2/iodine, respectively, with tetramethylurea. The structures of 1 and 3 were determined from single crystal X-ray diffraction data. 1 crystallizes in the triclinic space group P1 , with a = 809.9(1), b = 923.2(1), c = 1 374.6(1) pm, α = 106.80(1), β = 90.47(1), γ = 101.55(1)°; Z = 2; R = 0.045., 3 : monoclinic, P21/c, a = 1 311.4(1), b = 783.3(1), c = 1 409.1(1) pm, β = 97.36(1)°; Z = 4; R = 0.047. 1 and 3 are isolated neutral complexes with distorted tetrahedral coordination of iron. 3 is the first FeI3-complex with an O-donor ligand. The IR-spectra exhibit strong shifts of n?C = O and n?asC—N of tetramethylurea especially on coordinating to FeI3. 相似文献
988.
Humic substances were analysed by atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI) mass spectrometry in positive and negative modes. Using APCI the average m/z range of humic substances was reduced 5-fold compared to ESI. High-resolution time-of-flight mass spectrometry revealed the formation of multiply charged molecules in the ESI mode. Moreover, it was possible to obtain daughter ion mass spectra of humic substances by nanospray tandem mass spectrometry. The size-exclusion chromatography elution profile of humic substances was highly influenced by the pH of the analyte solution. By contrast, the pH had no significant influence on the observed mass spectra of humic substances. 相似文献
989.
The question of possible neutral intermediates which may lie on the reaction pathway in going from longifolene to isolongifolene has been investigated using BF3·Et2O-AcOD and D3PO4-dioxane, as reagents. It has been found that longicyclene is not an obligatory intermediate. The mode of cleavage of cyclopropane ring in longicyclene has been investigated. 相似文献
990.
Dialkylindium Acetates R2InOOCCH3 (R = CH3, C2H5). Preparation, Properties, and Structure. Dimethyl- and diethylindium acetate were prepared and the vibrational spectra (IR and RAMAN ) discussed. The X-ray structure determination shows that diethylindium acetate belongs to the orthorhombic space group Pnma. The unit cell with lattice constants a = 8.40, b = 7.41, c = 15.13 Å contains four molecules. Each indium atom forms with an acetate group a planar four-membered ring. The indium-oxygen distance within such a ring is only a little shorter than the distance of this oxygen to the indium of the next neighboured ring. Indium has therefore the coordination number six. 相似文献