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排序方式: 共有87条查询结果,搜索用时 15 毫秒
61.
S. L. Pentoney K. H. Shafer P. R. Griffiths R. Fuoco 《Journal of separation science》1986,9(3):168-171
The feasibility of supercritical fluid chromatography/Fourier transform-infrared (SFC/FT-IR) microspectrometry is presented. In this approach to SFC/FT-IR, the chromatographic eluates are aspirated from the restrictor directly onto the surface of a moving window which then passes into the beam focus of an infrared microscope. Because the mobile phase is gaseous at ambient conditions, elimination of the mobile phase is easily accomplished. Detection limits in all interfaces between a chromatograph and an FT-IR spectrometer in which the mobile phase is eliminated are determined in large part by the area over which the sample is deposited. We have shown that SFC eluates can be condensed at ambient temperature into spots of 100 to 200μm in diameter. The microscope interface therefore serves to increase the sensitivity of the SFC/FT-IR measurements of these spots and detection limits in the low nanogram range are possible. Preliminary results obtained before any real attempts were made to optimize the deposition process indicate that identifiable spectra can be obtained in real time at the 50 ng level for chromatographic separations performed with a 100μm i.d. wall coated open tubular column. Reproducible reconstructed chromatograms are obtained as each deposited eluate travels through the beam focus of the microscope. The concentration profile of deposited peaks was determined by IR measurements performed at 50 μm increments over the width of the peak to ascertain the deposition size. The results described in this paper, while not yet optimized, indicate the great potential of SFC/FT-IR microspectrometry. 相似文献
62.
A binary glass of thorium and hafnium tetrafluorides (with dopant concentrations of LaF3) has been investigated using EXAFS and XANES analysis of the LIll edge spectra of thorium. Results of EXAFS analysis indicate that there is no change in the number of nearest neighbors of thorium ions. However, the intensity of the white line in XANES is significantly higher in the glass. This increase in intensity has been explained semiquantitatively in terms of enhanced covalency of ThF bonding. Since the coordination number of Th4+ remains constant in both crystalline and glassy states, covalency enhancement seems to be a general characteristic of glassy state of ionic materials. 相似文献
63.
Plunkett S Parrish ME Shafer KH Shorter JH Nelson DD Zahniser MS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(11):2505-2517
Infrared absorption lines of hydrazine are broad and typically not baseline resolved, with line strengths approximately 100 times weaker than the more widely studied compound ammonia. Hardware and software improvements have been made to a two-color infrared tunable diode laser (IR-TDL) spectrometer in order to improve the limit of detection (LOD) of hydrazine (N2H4) in the cigarette smoke matrix. The detection limit in the smoke matrix was improved from 25 parts-per-million-by-volume (ppmv) to 4.2 ppmv using a 100 m pathlength cell with acquisition of background spectra immediately prior to each sample and 100 ms temporal resolution. This study did not detect hydrazine in cigarette smoke in the 964.4-964.9 cm(-1) spectral region, after mathematically subtracting the spectral contributions of ethylene, ammonia, carbon dioxide, methanol, acrolein, and acetaldehyde. These compounds are found in cigarette smoke and absorb in this spectral region. The LOD is limited by remaining spectral structure from unidentified smoke species. The pseudo random noise (root mean square) in the improved instrument was 2 x 10(-4) absorbance units (base e) which is equivalent to a 0.09 ppmv hydrazine gas sample in the multipass cell. This would correspond to a detection limit of 0.44 ppmv of hydrazine, given the dilution of the smoke by a factor of 5 by the sampling system. This is a factor of 10 less than the 4.2 ppmv detection limit for hydrazine in the smoke matrix, and indicates that the detection limit is primarily a result of the complexity of the matrix rather than the random noise of the TDL instrument. 相似文献
64.
J. Milton Harris Steven G. Shafer S. D. Worley 《Journal of computational chemistry》1982,3(2):208-213
Heats of formation calculated by MINDO /3 are reported for 42 carbocations for which experimental heats of formation have been published. Errors associated with these calculations can be large, with an overall range of ±13 kcal/mol. Correction of systematic errors in the MINDO /3 calculations by means of hydrocarbon models and isodesmic relationships results in a reduction in the range of errors to ±8 kcal/mol. Comparison with experimental heats of reaction of hydride transfer equilibria minimizes experimental errors and gives an average absolute error of 2 kcal/mol with a range of ±3 kcal/mol. 相似文献
65.
M Appel J J Freeman J S Gardner G H Hirasaki Q G Zhang J L Shafer 《Magnetic resonance imaging》2001,19(3-4):535-537
We report on experiments to characterize internal magnetic field gradients that are caused by magnetic susceptibility differences between the solid phase and the fluids filling the pore space. Our measurements focus on low-field relaxometry of brine and oil in sandstones from various reservoirs around the world. Our results show the need to understand the dependence of internal field gradients on diffusion length, pore size- and fluid distribution in order to predict the impact of internal gradients on the interpretation of NMR experiments. 相似文献
66.
We describe a mathematical approach based on homogenization theory toward representing the effects of mesoscale coherent structures on large-scale transport in the ocean. We demonstrate the approach on a deterministic and a random model flow. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
67.
McIntyre NR Lowe EW Belof JL Ivkovic M Shafer J Space B Merkler DJ 《Journal of the American Chemical Society》2010,132(46):16393-16402
Peptidylglycine α-amidating monooxygenase (PAM) is a bifunctional enzyme which catalyzes the post-translational modification of inactive C-terminal glycine-extended peptide precursors to the corresponding bioactive α-amidated peptide hormone. This conversion involves two sequential reactions both of which are catalyzed by the separate catalytic domains of PAM. The first step, the copper-, ascorbate-, and O(2)-dependent stereospecific hydroxylation at the α-carbon of the C-terminal glycine, is catalyzed by peptidylglycine α-hydroxylating monooxygenase (PHM). The second step, the zinc-dependent dealkylation of the carbinolamide intermediate, is catalyzed by peptidylglycine amidoglycolate lyase. Quantum mechanical tunneling dominates PHM-dependent C(α)-H bond activation. This study probes the substrate structure dependence of this chemistry using a set of N-acylglycine substrates of varying hydrophobicity. Primary deuterium kinetic isotope effects (KIEs), molecular mechanical docking, alchemical free energy perturbation, and equilibrium molecular dynamics were used to study the role played by ground-state substrate structure on PHM catalysis. Our data show that all Ν-acylglycines bind sequentially to PHM in an equilibrium-ordered fashion. The primary deuterium KIE displays a linear decrease with respect to acyl chain length for straight-chain N-acylglycine substrates. Docking orientation of these substrates displayed increased dissociation energy proportional to hydrophobic pocket interaction. The decrease in KIE with hydrophobicity was attributed to a preorganization event which decreased reorganization energy by decreasing the conformational sampling associated with ground state substrate binding. This is the first example of preorganization in the family of noncoupled copper monooxygenases. 相似文献
68.
Akimichi Takemura Vladimir Vovk Glenn Shafer 《Annals of the Institute of Statistical Mathematics》2011,63(5):873-885
We prove game-theoretic generalizations of some well-known zero-one laws. Our proofs make the martingales behind the laws
explicit, and our results illustrate how martingale arguments can have implications going beyond measure-theoretic probability. 相似文献
69.
A method employing solid-phase extraction coupled with HPLC separation of thiol-monobromobimane (mBBr) derivatives was developed and optimized to quantify dissolved thiols at concentrations as low as 0.1 nM for glutathione (GSH) and gamma-glutamylcysteine (gammaEC) in natural waters. The reducing reagent, tri-n-butylphosphine (TBP), is needed for complete derivatization. At the optimal addition of TBP ([TBP]/[mBBr] = -0.4-1.6), no interference from copper was observed. The thiol fluorescence signal was totally suppressed if the mole ratio of TBP to mBBr was 2.6 or greater. Consistent recovery of thiols standards in a NaCl solution (0.5 M) was obtained using the Waters HLB reversed-phase resin, and blank levels of GSH and gammaEC were extremely low (less than 0.03 nM). The detection limits for GSH, gammaEC and phytochelatin-2 (PC-2) were 0.03, 0.03, and 0.06 nM, respectively. 相似文献
70.
Dale M. Shafer 《School science and mathematics》1981,81(3):257-258