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991.
Reaction of optically active alpha-oxazolidinonylallenylstannanes with oxiranes in the presence of BF3.OEt2 produced beta-hydroxypropargylamines with high syn diastereoselectivity and high enantioselectivity through an initial Lewis-acid-catalyzed rearrangement of the oxirane to the corresponding aldehyde via an alkyl, aryl, or hydride shift. This permits the use of readily available oxiranes as alternatives to aldehydes that are difficult to prepare and/or unstable. 相似文献
992.
Louis Nadjo 《Journal of Electroanalytical Chemistry》1980,108(1):29-47
The electrochemical and photoelectrochemical behaviours of nCdTe and pCdTe singlecrystal semiconductors are investigated in acetonitrile solutions containing tetrabutylammonium tetrafluoroborate and various electroactive compounds, i.e. anthracene, phthalonitrile, nitromesitylene, 9-fluorenone, nitrobenzene, metatertiobutylnitrobenzene, benzoquinone and ferricenium tetrafluoroborate. The cyclic voltammograms at the semiconductor electrodes in the dark and illuminated with red light are compared to the Nernstian behaviour at a platinum disk electrode. The flat-band potential is estimated by using the photocurrent onset potential under continuous irradiation and Schottky-Mott plots. Consistent results have been obtained by these two methods. The usual band model is shown to predict roughly the observed behaviour of n- and pCdTe except for the cases where the presence of invisible films or surface states after polishing, and/or etching and/or the first reduction or oxidation voltammetric scan modifies the expected results. These surface modifications are capable of mediating electron transfer and explain the extension of photo effects far negative of the conduction band edge, using a 1.40-eV photon. 相似文献
993.
33S NMR chemical shifts were calculated by the scaled DFT and EMPI approaches for the fluoride, chloride and bromide of trimethylsulfonium ion (1) and S-methyltetrahydrothiophenium ion (2), in addition to the free cations. Experimental values were obtained for the iodides of 1 (delta +48, CS2 = 0 ppm) and 2 (delta +95), and were found to agree with the calculated values well within the standard deviation of 35 ppm (3.5% of the shielding range) established in earlier work for a great variety of sulfur compounds. An earlier literature value of delta +750 for the iodide of 2 is therefore to be replaced. Calculations provide a shift of delta +68 for S-methylthianium ion with equatorial methyl, indicating that the reported value of delta +670 for the iodide is also incorrect. 相似文献
994.
A multiparametric curve-fitting procedure is described for locating the equivalence point of a potentiometric titration and is applied to data obtained in titrations of acetate ion with hydrochloric acid over a wide range of concentrations (down to 6.5 · 10-5M acetate). It does not depend on the existence of a point of inflection on the titration curve, and therefore yields useful results in titrations of this very weak base at concentrations well below that at which the point of maximal slope disappears. Three parameters are involved: the concentration of the base being titrated, the concentration dissociation constant Ka of its conjugate acid in the medium employed, and the apparent activity coefficient yH+ of hydrogen ion in that medium, and all three of these must be evaluated when a new supporting electrolyte is employed. In 3.0 M potassium chloride at 24°, the apparent activity coefficient of hydrogen ion is 1.7460, and this value permits data obtained in titrations of other or unknown bases in this medium to be interpreted by two-parameter fits. The value of Ka for acetic acid in this medium is 1.3134 · 10-5M; by means of these two numerical values routine titrations of acetate in this medium can be interpreted by one-parameter fits. It is possible to locate the equivalence point with an accuracy and a precision that cannot be approached by other techniques and even to obtain useful and reliable results under conditions so unfavorable that other techniques fail completely. 相似文献
995.
Wagg LM Hornyak GL Grigorian L Dillon AC Jones KM Blackburn J Parilla PA Heben MJ 《The journal of physical chemistry. B》2005,109(20):10435-10440
Gas feed composition and reaction temperature were varied to identify the thermodynamic threshold conditions for the nucleation and growth of SWNT from methane on supported Fe/Mo catalyst. These reaction conditions closely approximate the pseudoequilibrium conditions that lead to the nucleation and growth of SWNT. These measurements also serve to determine an upper limit of the Gibbs free energy of formation for SWNT. The Gibbs free energy of formation relative to graphite is in good agreement with literature values predicted from simulations for SWNT nuclei containing approximately 80 atoms, while considerably larger than that predicted for bulk (5,5) SWNT. Our estimate over the range 700 to 1000 degrees C of 16.1 to 13.9 kJ mol(-1) falls between the results of these simulations and literature values for diamond. 相似文献
996.
Prior work had shown that the principal products of the pyrolysis of p-terphenyl are biphenyl and certain higher polyphenyls. Since the three terphenyls as well as particular higher polyphenyls are being investigated as heat transfer media for atomic energy reactors, the determination of biphenyl, as a major or minor product of their pyrolysis, becomes of prime importance in order to follow the trend of reaction products.Because of the greater solubility of biphenyl in water, as compared to other polyphenyls, biphenyl is completely extracted from such mixtures by water and can be determined spectrophotometrically in aqueous solution. Effects of temperature, rates of solution, and the presence of polyphenyls were studied. The solubility of biphenyl is about 0.9 mg/100 ml of water, but the suggested working limit in 0.4 mg biphenyl/100 ml of solvent.As little as 0.1% biphenyl in p-terphenyl may be detected and as high as 20% may be determined in higher polyphenyls. 相似文献
997.
Willey TM Vance AL Bostedt C van Buuren T Meulenberg RW Terminello LJ Fadley CS 《Langmuir : the ACS journal of surfaces and colloids》2004,20(12):4939-4944
Thioctic acid (alpha-lipoic acid) is a molecule with a large disulfide-containing base, a short alkyl chain with four CH2 units, and a carboxyl termination. Self-assembled monolayer (SAM) films ofthioctic acid adsorbed on Au(111) have been investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to determine film quality, bonding, and morphology. Using standard preparation protocols for SAMs, that is, dissolving thioctic acid in ethanol and exposing gold to the solution, results in poor films. These films are highly disordered, contain a mixture of carboxyl and carboxylate terminations, have more than monolayer coverage, and exhibit unbound disulfide. Conversely, forming films by dissolving 1 mmol thioctic acid into 5% acetic acid in ethanol (as previously reported with carboxyl-terminated alkanethiols) forms ordered monolayers with small amounts of unbound sulfur. NEXAFS indicates tilted over endgroups with the carboxyl group normal on average 38 degrees from the surface normal. Slight angle-dependent intensity modulations in other features indicate alkyl chains statistically more upright than prostrate on the surface. Reflection-absorption Fourier transform infrared (RA-FTIR) spectra indicate hydrogen bonding between neighboring molecules. In such well-formed monolayers, a stark reorientation occurs upon deprotonation of the endgroup by rinsing in a KOH solution. The carboxylate plane normal is now about 66 degrees from sample normal, a much more upright orientation. Data indicate this reorientation may also cause a more upright orientation to the alkyl portion of the molecules. 相似文献
998.
Wolfgang Robien Louis Hellemans Peter Wolschann 《Monatshefte für Chemie / Chemical Monthly》1980,111(3):779-782
Consistent force field calculations on the geometry of triethylamine are presented and compared with experimental results. Triethylamine seems to exist mainly in a conformation with all ethyl groupscis to the lone pair electrons at the nitrogen atom.
Kraftfeldberechnungen der Geometrie von Triethylamin (Kurze Mitteilung)
Zusammenfassung Consistent Force Field Rechnungen der Geometrie von Triethylamin werden mit experimentellen Ergebnissen verglichen. Triethylamin existiert dann in der günstigsten Konformation, wenn alle Ethylgruppencis zum einsamen Elektronenpaar des Stickstoffs stehen.相似文献
999.
1000.
It is shown that the use of spectrophotometric cells having circular cross sections leads to errors that depend on the absorbance, on the ratio of beam width to cell diameter, and on the distance between the center of the beam and the diameter of the cell, but that the nature and magnitude of these errors render them essentially undetectable in practical analytical work. 相似文献