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81.
The reaction of α,β-unsaturated acylsilanes with allenylsilanes can be directed to produce either five or six-membered carbocyclic compounds. 相似文献
82.
David J. Williams 《Tetrahedron》1980,36(24):3571-3577
An X-ray study of the major product of the intramolecular Diels-Alder reaction of the diene-anhydride (2) has confirmed it as being the desired cytochalasan analogue (3). In particular the cyclisation has been regioselective, and has taken place via the endo transition state to generate the adduct with the correct relative configurations at the four chiral centres. Details of the conformational geometry of (3) are discussed. 相似文献
83.
We have investigated the dielectrophoretic assembly of colloidal gold, carbon black, and carbon nanotubes into electrical wires. The resulting microwires have diameters less than 1 microm, with lengths ranging from 5 microm to 3 mm. Current-voltage curves for these wires indicate an ohmic response, where the resistance is determined by the type of colloid and by the frequency of the alternating field used to grow the wires. The predicted frequency dependence of dielectrophoresis is confirmed by experiment. Measurements of the threshold voltage for initial wire growth are also presented. These experiments demonstrate that a variety of nanoparticles can be assembled into microwires for sensor applications. 相似文献
84.
Buckley N Maltby D Burlingame AL Oppenheimer NJ 《The Journal of organic chemistry》1996,61(8):2753-2762
The relative rates for the gas-phase dissociation RX(+) --> R(+) + X degrees of five (4-Y-substituted benzyl)dimethysulfoniums (Y = MeO, Me, H, Cl, and NO(2)) and 24 (4-Y-substituted benzyl)-3'-Z-pyridiniums (complete series for Z = CN, Cl, CONH(2), and H, and 4-methoxy- and 4-nitrobenzyls for Z = F and CH(3)CO) were measured using liquid secondary ion mass spectrometry. The Hammett plot (vs deltaDeltaG degrees or sigma(+)) is linear for the sulfoniums, but plots for the four pyridinium series have a drastic break between the 4-Cl and 4-NO(2) substrates. Br?nsted-like plots for the pyridiniums show a strong leaving group effect only for 4-nitrobenzyls. An analysis of these linear free energy relations with supporting evidence from semiempirical computations suggests that collisionally activated pyridinium substrates dissociate by two pathways, direct dissociation and through an ion-neutral complex intermediate. Comparison of these results with results for the solution reactions of some of these compounds shows that the mechanism is different in the gas and solution phases. Sufficient experimental data are not available to assign a mechanism for dissociation to the sulfonium series, but computational results show characteristics of a direct dissociative mechanism. 相似文献
85.
David A. Pearlman 《Journal of computational chemistry》1994,15(1):105-123
The convergence behavior of free energy calculations has been explored in more detail than in any previously reported work, using a model system of two neon atoms in a periodic box of water. We find that for thermodynamic integration-type free energy calculations as much as a nanosecond or more molecular dynamics sampling is required to obtain a fully converged value for a single λ point of the integrand. The concept of “free energy derivatives” with respect to the individual parameters of the force field is introduced. This formalism allows the total convergence of the simulation to be deconvoluted into components. A determination of the statistical “sampling ratio” from these simulations indicates that for window-type free energy calculations carried out in a periodic waterbox of typical size at least 0.6 ps of sampling should be performed at each window (0.7 ps if constraint contributions to the free energy are being determined). General methods to estimate and reduce the error in thermodynamic integration and free energy perturbation calculations are discussed. We show that the difficulty in applying such methods is determining a reliable estimate of the correlation length from a short series of data. © 1994 by John Wiley & Sons, Inc. 相似文献
86.
Gottfried Lichti Brian S. Hawkett Robert G. Gilbert Donald H. Napper David F. Sangster 《Journal of polymer science. Part A, Polymer chemistry》1981,19(4):925-938
Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments. 相似文献
87.
The synthesis of complexes of the type π-C5H5Mo(CO)2LX and π-C5H5Mo(CO)L2X, where XCl, Br, or I and LP(OCH2)3CR (RCH3, C2H5, or C3H7), is reported. Infrared and conductance data verified that all compounds existed as covalent species in solution. Each of the three π-C5H5Mo(CO)2LCl complexes was isolated as an inseparable mixture of cis and trans isomeric forms. Only the trans forms of the remaining π-C5H5Mo(CO)2LX complexes were observed in solution, as indicated by infrared and PMR spectra. All of the π-C5H5Mo(CO)L2X compounds apparently exist in primarily one isomeric form in solution; their PMR spectra, which exhibited a sharp triplet resonance for the ?OCH2? protons of the phosphite ligands and a single sharp π-C5H5 proton signal, indicated a predominantly trans arrangement of the phosphite ligands at room temperature. 相似文献
88.
Palladium[0]-mediated Ullmann cross-coupling of 1-bromo-2-nitrobenzene (1 R = H) and its derivatives with a range of beta-halo-enals, -enones, or -esters readily affords the corresponding beta-aryl derivatives, which are converted into the corresponding quinolines, 2-quinolones, phenanthridines, or 6(5H)-phenanthridinones on reaction with dihydrogen in the presence of Pd on C or with TiCl(3) in aqueous acetone. [reaction: see text] 相似文献
89.
90.
Hercules DM 《Analytical and bioanalytical chemistry》1996,355(3-4):209-215
Use of X-ray Photoelectron Spectroscopy (XPS) for quantitative surface analysis is reviewed. Examples chosen are from our research on heterogeneous catalysts. XPS is useful for measuring distributions of oxidation states because of significant chemical shifts for many elements. However, linewidths complicate analysis of mixtures, necessitating the use of data analysis methodology. Use of factor analysis or deconvolution with non-linear least squares curve fitting gives useful protocols. Five important questions are posed, and some examples of solutions are presented: 1) How many components are present? 2) Where are they located? 3) What do they look like? 4) How much of each component is present? 5) How good is the answer? 相似文献