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51.
A statistical study of the potential dependence of a transfer coefficient supports the Marcus theory
A.M. Bond P.J. Mahon E.A. Maxwell K.B. Oldham C.G. Zoski 《Journal of Electroanalytical Chemistry》1994,370(1-2)
Cyclic voltammograms for the reduction of 2-methyl-2-nitropropane at a mercury electrode in acetonitrile solvent have been analyzed carefully by the “global” method. The dependence of the logarithm of the heterogeneous rate constant on the potential is only mildly parabolic, but statistical analysis shows that the curvature is nonetheless genuine and cannot be explained by random errors. The sign of the curvature is that predicted by the Marcus theory and the magnitude of the effect is also compatible with theory. No trend with scan rate is observed in any of the measured kinetic, thermodynamic or transport parameters. 相似文献
52.
Bose-Einstein condensation in a gas of sodium atoms 总被引:2,自引:0,他引:2
Davis KB Mewes M Andrews MR van Druten NJ Durfee DS Kurn DM Ketterle W 《Physical review letters》1995,75(22):3969-3973
53.
Amin Ibrahim Philip B. Oldham Terrance E. Conners Tor P. Schultz 《Microchemical Journal》1997,56(3):393-402
FT-Raman spectroscopy is used for the rapid measurement of wood pulp lignin. A total of 23 western softwood pulp samples with known kappa numbers (10–38) are used. Each sample is divided into three portions and scanned separately. The integrated area of the lignin band at approximately 1600 cm−1is ratioed against the integrated area of the cellulose bands in the 1200–1010 cm−1region and correlated to known kappa numbers. The measured ratios behave linearly with the kappa number (r= 0.99) and can be reproducibly determined with an error of approximately 2% or less. The data are presented and discussed in view of the potential for at-line analysis of lignin associated with chemical delignification of wood pulp. 相似文献
54.
Keith B. Oldham 《Journal of Solid State Electrochemistry》1998,2(6):367-377
When insoluble insulating crystals adhere to an electrode, the three-phase junction – where electrolyte solution, electrode
and crystal meet – is the only feasible site for an electrochemical reaction. Moreover, sustained reaction is possible only
if ions from the electrolyte solution are able to enter the crystal through the three-phase junction and disperse within the
crystal. Here, order-of-magnitude calculations demonstrate that diffusion to the three-phase junction is well able to support
voltammetry under standard experimental conditions. A model is built for cases of adherent cubes of uniform size and thereby
the shapes of chronoamperograms, chronograviograms and cyclic voltammograms are predicted. The model assumes that the ion
concentration at the three-phase junction plays a crucial role in the voltammetry, being determined by quasi-steady-state
ion diffusion from the bulk, the thermodynamics of the electrode reaction, and the extent to which the crystal has already
undergone reaction. Depending on the crystal size and scan rate, cyclic voltammograms may mimic solution-phase voltammograms
from classical thin-layer experiments or from typical stripping experiments. The effect of size heterogeneity on cyclic voltammetry
is simulated for lognormal distributions.
Received: 5 January 1998 / Accepted: 17 April 1998 相似文献
55.
C. C. Hayward G. Oldham A. R. Ware 《Journal of Radioanalytical and Nuclear Chemistry》1971,7(2):341-346
The feasibility and advantages of fast neutron activation analysis in a non-aqueous flowing system, using economical irradiation
techniques are outlined. The application of the method to the determination in solution of elements producing isotopes with
half lives in the range 588—29.4 sec, the selection of the optimum flow rate to minimise interferences for each element, and
their limits of detection are also given. A method for the prediction of the optimum flow rate, on a given system, for the
determination of any element producing an isotope of known half life is also given. 相似文献
56.
Steady-state voltammetry has been practised for decades but its use has recently been stimulated by the increasing popularity and availability of microelectrodes. This review concentrates on steady states obtained with the use of microelectrodes. After a general introduction, detailed discussions are given for steady-state voltammetry at hemispherical, inlaid disc, and ring electrodes, which are the most popular geometries that engender steady states. Ohmic polarization in steady-state voltammetry is also considered. Applications in analytical, kinetic and other studies are described. 相似文献
57.
Bowmaker GA Hanna JV Hahn FE Lipton AS Oldham CE Skelton BW Smith ME White AH 《Dalton transactions (Cambridge, England : 2003)》2008,(13):1710-1720
Single-crystal structural characterizations confirm the existence of the unusual 1 : 4 copper(I) halide : unidentate ligand adducts [Cu(CNt-Bu)4]X for X = Cl, Br (two forms), I (the chloride and one form of the bromide being solvated) with crystal packing dominated by stacks of interleaving cations. Cu-C range between 1.941(2) and 1.972(4) A. The structure of the 1 : 2 chloride complex is also recorded, being [ClCu(CNt-Bu)2], with the copper(I) atom environment trigonal planar, while CuCN : (CNt-Bu) (1 : 1) is a single-stranded polymer which spirals about a crystallographic 3-axis (CN scrambled), the ligands being pendant from the ...CuCNCuCN... string. The (5Cu static broadline NMR spectra of [Cu(CNt-Bu)4]I and [Cu(CNt-Bu)4]Br.H2O in the solid state exhibit dominant, narrow -1/2 <--> +1/2 central transition resonances and associated +/-1/2 <--> +/-3/2 satellite transition resonances which are characteristic of first-order quadrupole broadened systems, while associated high-resolution 65Cu MAS NMR data provide accurate measurement of the 65Cu isotropic chemical shifts. Both approaches provide complete data on the quadrupole and chemical shift interactions which contribute to these spectra. Far-IR spectra of products of reactions involving a range of CuX : t-BuNC ratios reveal the existence of 1 : 1.5 adducts for X = Br, I. Metal-carbon and metal-halogen bands are assigned in the far-IR spectra, which indicate a binuclear double halogen-bridged structure for the 1 : 1.5 complexes. 相似文献
58.
The conventional method of measurement in 14 MeV activation analysis is to employ gamma-ray spectrometry. The method has the
advantage of good selectivity but this is at the expense of sensitivity. In order to improve sensitivity the authors have
employed Cerenkov counting techniques and by the careful use of absorbers in a specially designed cell together with double
decay procedures have still retained a considerable degree of selectivity. The method has been applied to neutron flux measurement
and to the majority of the elements in the periodic table. 相似文献
59.
60.
Schaaf O Jarvis AP van der Esch SA Giagnacovo G Oldham NJ 《Journal of chromatography. A》2000,886(1-2):89-97
Based on reversed-phase high-performance liquid chromatography (RP-HPLC) and atmospheric pressure chemical ionization (APCI) mass spectrometry, a HPLC-MS method was developed to permit the rapid qualitative and quantitative analysis of azadirachtin and related tetranortriterpenoids from seeds and tissue cultures of Neem (Azadirachta indica). APCI+ standard scanning mass spectra of the major Neem triterpenoids were recorded and utilized to select suitable ions for selected ion monitoring (SIM). Transitions for selective reaction monitoring (SRM) were based on MS-MS experiments. Using SIM, major Neem triterpenoids were detected in callus culture material and seed kernels of A. indica. The limit of detection for azadirachtin in extract samples (approximately 1 ng ml(-1) or 10 pg in SIM mode) was determined to be (with respect to injected absolute amounts) approximately 1000-times lower than values quoted in the literature for existing HPLC methods (approximately 200 ng ml(-1) or 10 ng). In addition to high sensitivity, the HPLC-MS method is able to tolerate minimal sample preparation and purification, dramatically reducing total analysis time. 相似文献