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211.
Meier MA de Gans BJ van den Berg AM Schubert US 《Rapid communications in mass spectrometry : RCM》2003,17(20):2349-2353
Recently, a new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample spotting technique for poly(ethylene glycol), offering improved analysis possibilities, was described. In this contribution the application of ink-jet printing to automated, multiple-layer MALDI-TOFMS sample preparation of synthetic polymers is presented, allowing accurate deposition of matrix, additive and analyte solutions. The new sample preparation technique was evaluated for poly(ethylene glycol) as well as poly(methyl methacrylate) standards, and optimized settings for both synthetic polymers have been obtained. 相似文献
212.
Michael SchwarzPeter Winterhalter 《Tetrahedron letters》2003,44(41):7583-7587
Anthocyanins, isolated from natural sources by countercurrent chromatography, were reacted with cinnamic acids bearing at least one electron-donating substituent at the para-position. The resulting pyranoanthocyanins obtained by this simple one-step reaction were much less susceptible to pH shifts and retained their original colour over a wide pH-range. Through reaction with p-dimethylamino cinnamic acid, synthetic malvidin- and cyanidin-based anthocyanins with a unique violet hue were prepared. 相似文献
213.
[reaction: see text] A new method to facilitate the separation of diastereomeric syn- and anti-1,3-diols is described. The method relies on the different hydrolysis rates of the corresponding diastereomeric acetonides. Treatment of a dichloromethane solution of syn- and anti-1,3-diol-acetonide with a catalytic amount of diluted aqueous hydrochloric acid leads to the selective cleavage of the anti diastereomer. The resulting anti-1,3-diol can be easily separated from the unchanged syn-1,3-diol-acetonide. 相似文献
214.
Thomas Geiger Richard Nottenberg Mary-Lou Plaprat Michael Grtzel 《Helvetica chimica acta》1982,65(8):2507-2516
Light-induced interfacial electron transfer from two p-InP electrodes differing in the amount of majority carrier doping to a number of electron relays ( R ) dissolved in aqueous solution was investigated. The material with the lower carrier density (0.71 × 1018 cm?3) exhibited much better wavelength response and quantum yield for electron transfer than the electrode doped with 2.3 × 1018 cm?3 charge carriers. Using cobalt (III) sepulcrate, Co (sep)3+, as an electron relay a polychromatic light to electrical energy conversion efficiency of 18% was obtained. The potential of this relay for use in a regenerative photoelectrochemical cell is briefly discussed. 相似文献
215.
Jianfu Ding Futian Liu Mei Li Michael Day Ming Zhou 《Journal of polymer science. Part A, Polymer chemistry》2002,40(23):4205-4216
The polycondensation of decafluorobenzophenone with hexafluorobisphenol A was modified by the addition of a molecular sieve dehydrating apparatus to the refluxing reaction system. This modification promoted the polymerization and enabled the reactions to be conducted in milder conditions and completed in a shorter time, thereby depressing side reactions such as branching and crosslinking. The resulting fluorinated poly(arylene ether ketone)s (FPAEK) were free of gel particles and possessed the designed molecular weights. This modified procedure was also suitable for introducing crosslinkable pentafluorostyrene (FSt) moieties into the polymers at the chain ends and/or inside the chain with the vinyl group of FSt being pendant. The resulting FSt containing fluorinated poly(arylene ether ketone)s (FPAEK‐FSt) can then be thermally crosslinked at 100 °C in the presence of 1% benzoyl peroxide (BPO) or at 250 °C without any initiator. The glass‐transition temperatures (Tg's) of FPAEK increased with increasing molecular weight and leveled off at about 147 °C for the polymer with a number‐average molecular weight of 18,600 Da, whereas the values were not apparently affected by the addition of FSt units. However, crosslinking of the FPAEK‐FSt resulted in an approximate 30 °C increase of the Tg. Spin‐coating FPAEK‐FSt onto silicon wafers followed by crosslinking gave films with excellent thermal stability, physical strength, and adhesion to the substrate as well as good reproducibility in terms of film preparation and optical properties. The refractive index and birefringence of the films measured at a wavelength of 1.55 μm were 1.502 and 2.5 × 10?3, respectively. © 2002 Government of Canada. Exclusive worldwide publication rights in the article have been transferred to Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4205–4216, 2002 相似文献
216.
Clemens C. Freyhardt Michael Wiebcke Jürgen Felsche Günter Engelhardt 《Journal of inclusion phenomena and macrocyclic chemistry》1994,18(2):161-175
Single-crystal X-ray structure analyses of N(nPr)4[B5O6(OH)4][B(OH)3]2,1, and N(nBu)4 [B5O6(OH)4][B(OH)3]2,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B5O6(OH)4]– ionsand B(OH)3 molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr)
4
+
and N(nBu)
4
+
ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP21/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both11B and13C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence.
Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages). 相似文献
217.
Ab initio molecular orbital calculations with a double-ζ basis have been carrried out on five models of beryllocene, Cp2Be, with fixed geometries. The lowest energies are obtained for the π-Cp, σ-Cp and D5d models.
The He(I) photoelectron spectrum of Cp2Be was recorded and the ionization potentials of the first bands were compared with the orbital energies obtained from the molecular orbital calculations. A satisfactory fit between experiment and calculations was obtained for a slip sandwich model of Cs symmetry. A model of C5v symmetry is only compatible with the PE spectrum if the Jahn—Teller splitting of the lowest 2E1 state of the molecular ion is exceptionally large, 1.0 eV. 相似文献
218.
The vertical ionization potentials of bis(-allyl)nickel (see (1) in Fig. 1) are calculated by means of the Green's function approach within a semiempirical INDO extension to the first transition metal series. The computed ionization potentials are in good agreement with an experimentally deduced assignment. In contrast to earlier theoretical and experimental studies, the 7a
u
() level is predicted on top of the levels corresponding to the Ni 3d orbitals. Our approach leads to a complete assignment of the PE spectrum of (1) in the outer valence region. 相似文献
219.
Several aromatic compounds containing one or two C6F5S groups have been prepared by nucleophilic displacement reactions using CuSC6F5 in DMF solution. Aromatic iodine or bromine, rather than chlorine of fluorine is replaced by the SC6F5 group using CuSC6F5. A mechanism is postulated. New compounds prepared include -(C6F6F5S)2C6H4, - and -(C6F5S)2C6F4 and XC6H4SC6F5(X=C1, NO2, I, CH3, CO2C2H5). 相似文献
220.
Abstract— The aerobic dye-sensitized photooxygenation of monohydric phenols proceeds by way of singlet oxygen under the conditions studied. Various phenols give different proportions of reaction with and quenching of singlet oxygen. Para-substituted 2,6-di-t-butylphenols show a linear correlation between the log of the total rate of singlet oxygen removal and their halfwave oxidation potentials; the same correlation is given for certain phenol methyl ethers. A Hammett plot using s?+ gives ρ - 1.72 ± 0.12, consistent with development of some charge in the quenching step. Reaction of photo-chemically generated singlet oxygen with 2,4,6-triphenylphenol gives 2,4,6-triphenylphenoxy radical as an intermediate in singlet oxygen quenching, although no overall reaction occurs. Kinetic analysis indicates that the radical is derived exclusively from the interaction of 2,4,6-triphenylphenol with singlet oxygen. A charge-transfer mechanism for quenching of singlet oxygen by phenols is proposed. 相似文献