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51.
Hevia E Pérez J Riera V Miguel D Campomanes P Menéndez MI Sordo TL García-Granda S 《Journal of the American Chemical Society》2003,125(13):3706-3707
As depicted in the scheme, the alkylidenamido complex 1, a N-rhenaimine, reacts with ketenes to afford the beta-lactams 2-4, which possess a {Re(CO)3(bpy)} fragment as substituent at nitrogen. Clean demetalations using HOTf or MeOTf yield the free beta-lactams or N-methyl-beta-lactams along with [Re(OTf)(CO)3(bpy)]. DFT calculations help to rationalize why the reaction is faster than those of non transition metal N-substituted imines. 相似文献
52.
Villareal V Kaddis J Azad M Zurita C Silva I Hernandez L Rudolph M Moran J Gomez FA 《Analytical and bioanalytical chemistry》2003,376(6):822-831
Partial-filling affinity capillary electrophoresis (PFACE) is used to examine the binding interactions between two model biological systems: D-Ala-D-Ala terminus peptides to the glycopeptide antibiotic vancomycin (Van) from Streptomyces orientalis, and arylsulfonamides to carbonic anhydrase B (CAB, EC 4.2.1.1, bovine erythrocytes). Using these two systems, modifications in the PFACE technique are demonstrated including flow-through PFACE (FTPFACE), competitive flow-through PFACE (CFTPFACE), on-column ligand synthesis PFACE (OCLSPFACE), and multiple-step ligand injection PFACE (MSLIPFACE). In PFACE small plugs of sample are injected into the capillary column and an equilibrium is established between receptor and ligand during electrophoresis. Binding constants are then obtained by Scatchard analysis using changes in the migration time of the receptor/ligand on changing the concentration of the ligand/receptor. Data demonstrating the quantitative potential of these methods are presented. This review focuses on the unique capabilities of the different PFACE techniques as applied to two model biological systems. 相似文献
53.
Rosa Maria Rojas K. Petrov G. Avdeev J. M. Amarilla L. Pascual J. M. Rojo 《Journal of Thermal Analysis and Calorimetry》2007,90(1):67-72
Chromium doped spinels LiCrYMn2−YO4 (0.2≤Y≤0.8) has been synthesized by the sucrose-aided combustion procedure. The thermal behaviour, phase homogeneity and structural
characteristics of the samples were studied by thermal analysis, coupled mass spectrometry, and room-and high-temperature
X-ray diffraction methods. It was found that the ‘as prepared’ samples contained residual organic impurities undetectable
for X-ray diffraction, that burn out completely at 400°C. Samples treated between 400 and 750°C are single phase spinels,
whose crystallites size increase from 10 to 50 nm on increasing the temperature. Cr-doping enhances the thermal stability
of the spinels, which augments on increasing the Cr content Y. The enhanced thermal stability of the spinels has been accounted
for based on the high excess stabilization energy of Cr3+ in octahedral ligand field. 相似文献
54.
Samuel González-Mancebo Javier Lacadena Yolanda García-Alonso Jesús Hernández-Benito Emilio Calle Julio Casado 《Monatshefte für Chemie / Chemical Monthly》2002,133(2):157-166
Summary. Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of
the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction
was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO+/NO2H2
+ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron
donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly
by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.
Received July 13, 2001. Accepted (revised) September 18, 2001 相似文献
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57.
Octavio Surez-Iglesias Ignacio Medina Consuelo Pizarro Julio L. Bueno 《Fluid Phase Equilibria》2007,260(2):279-286
The Taylor–Aris chromatographic technique was employed for the determination of diffusion coefficients of 2-fluoroanisole, 2-bromoanisole, allylbenzene and 1,3-divinylbenzene at infinite dilution in supercritical carbon dioxide from 313.16 to 333.16 K and pressures between 15 and 35 MPa. As expected, the diffusivities rise when temperature increases and pressure decreases. Numerous predictive equations are compared with experimental data: Lai–Tan, Liu–Ruckenstein cluster formula, Woerlee, Hippler–Schubert–Troe, Catchpole–King, Eaton–Akgerman, He, He–Yu, Liu–Silva–Macedo, Funazukuri and coworkers, Dariva–Coelho–Oliveira, Zhu–Lu–Zhou–Wang–Shi and the Liu–Ruckenstein RHS formula. The equations of He, He–Yu and Catchpole–King are the best of all, but cannot be used in the whole range of temperatures and solvent densities. 相似文献
58.
59.
Summary The reduction of nickel(II) halides with NaBH4 in the presence of different ligands, L=PPh3, AsPh3, SbPh3, has been studied. With a molar ratio L/Ni=3, new complexes NiX(SbPh3)3, X=Cl, Br, I, were obtained. With a molar ratio L/Ni=2, dimeric species [NiXL2]2, X=Cl, Br, I; L=PPh3, AsPh3, SbPh3, were isolated. They are unstable and decompose easily in the solid and rapidly in solution, so that pure samples were only identified for X=Cl, L=PPh3, AsPh3, SbPh3; X=Br, L=PPh3 and X=I, L=PPh3. With a molar ratio L/Ni=1, complexes [NiXL]n (probably polymeric) were obtained. They are very unstable and pure samples could only be isolated when X=Cl, L=PPh3. Impure substances containing variable amounts of decomposition products were obtained in all the remaining cases. The chemical and structural behaviour of these complexes is discussed. 相似文献
60.
Julio Belmar Claudio Jimnez C. Ruiz‐Prez F. S. Delgado Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):o599-o601
In the title compound, C15H20N2O, the bond distances and angles are consistent with the presence of the hydroxy tautomer. This tautomer was unambiguously determined by the clear presence of a H atom bonded to oxygen, as well as the total absence of any residual electron density around the N atom in the heterocycle, thus precluding any possibility of desmotropism. 相似文献