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951.
952.
(+)-Thalictrifoline () has been synthesized from an optically resolved (+)-8-oxo-13-carboxytetrahydroprotoberberine () whose absolute configuration was established by correlation with (+)-. This determines the absolute configurations of (+)-thalictrifoline () as 13R, 14R aria (+)-corydalic acid methyl ester () as 3R, 4R. 相似文献
953.
Studies on the electron transfer (ET) interaction of 1,4-dihydroxy-9,10-anthraquinone and 6,11-dihydroxy-5,12-naphthacenequinone with aliphatic and aromatic amine (AlA and ArA, respectively) donors have been investigated in acetonitrile solutions. Steady-state (SS) measurements show quenching of the quinone fluorescence by amines, without indicating any change in the shape of the fluorescence spectra. No significant change in the absorption spectra of the quinones is also observed in the presence of the amines. For all the quinone-amine pairs, the bimolecular quenching constants (kq) estimated from SS and time-resolved measurements are found to be similar. Variation in the kq values with the oxidation potentials of the amines indicates the involvement of the ET mechanism for the quenching process. A reasonably good correlation between the kq values and the free energy changes (deltaG0) for the ET reactions following Marcus' outer-sphere ET theory also supports this mechanism. It is seen that for both the quinone-ArA and quinone-AlA systems, the kq values initially increase and then get saturated at some diffusion-controlled limiting values (kqDC) as deltaG0 values gradually become more negative. Interestingly, however, it is seen that the kqDC value for the quinone-AlA systems is substantially lower than that for quinone-ArA systems. Such a large difference in the kqDC values between quinone-AlA and quinone-ArA systems is quite unusual. Present results have been rationalized based on the assumption that an orientational restriction is imposed for the encounter complexes in quinone-AlA systems to undergo ET reactions, which arises because of the localized (at amino nitrogen) shapes of the highest-occupied molecular orbitals (HOMO) of AlA in comparison to the pi-like HOMO of the ArA. 相似文献
954.
Nath S Ghosh SK Panigrahi S Pal T 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(9):2145-2151
In this report, selenious acid (H2SeO3) has been exploited to study the decolorization of a cationic dye, dimethylmethylene blue (DMMB) with UV-light. Micelles have effectively been employed as organized media to promote the rate of decolorization of the dye molecules. Micellar catalysis has been explained as a consequence of electrostatic, hydrophobic and charge transfer interactions. It has also been shown that strong charge transfer and electrostatic interaction lead to an appreciable enhancement of the reaction rate in micelle, whereas, weak hydrophobic interaction is of marginal importance. Existence of monomer-dimer equilibrium for the dye molecules under certain selective environments has been identified spectrophotometrically. Then the shift of dimer-monomer equilibrium of the dye has been successfully studied in aqueous and micellar environments exploiting photodecolorization process for the dye in solution. 'Salting-in' and 'salting-out' agents were introduced into the reaction mixture to examine the viability of the dye decolorization process for dye contaminated water samples. 相似文献
955.
Vijay Kumar 《Tetrahedron letters》2006,47(39):7001-7005
Highly selective and efficient Michael additions of heterocyclic enamines, viz. indoles, pyrroles, and pyrazoles with α,β-unsaturated olefins using 2 mol % of ZrCl4 has been achieved. 相似文献
956.
Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt–CH3 fragments in ∼5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield. The deuteration can be reversed by dissolution in CH3OH or CD3OH. Kinetic analysis and isotope effects, together with support from density functional theory calculations indicate a metal–ligand cooperative mechanism wherein DPK enables Pt–CH3 deuteration by allowing non-rate-limiting protonation of PtII by CD3OD. In contrast, other model di(2-pyridyl) ligands enable rate-limiting protonation of PtII, resulting in non-rate-limiting C–H(D) reductive coupling. Owing to its electron-poor nature, following complete deuteration, DPK can be dissociated from the PtII-centre, furnishing [(CD3)2PtII(μ-SMe2)]2 as the perdeutero analogue of [(CH3)2PtII(μ-SMe2)]2, a commonly used PtII-precursor.Di(2-pyridyl)ketone dimethylplatinum(ii), (dpk)PtII(CH3)2, reacts with CD3OD at 25 °C to undergo complete deuteration of Pt–CH3 fragments in ∼5 h without loss of methane to form (dpk)PtII(CD3)2 in virtually quantitative yield. 相似文献
957.
The whole plant of Ajuga bracteosa afforded five compounds including one new clerodane diterpenoid designated as Bracteonin-A (1) 6alpha-acetoxy, 15 (R&S)-methoxy, 18-(4'-hydroxy, 3'-beta-methyl, 3'-alpha-acetoxy, butyryloxy) neoclerodane. The other compounds identified were 14,15-dihydroajugapitin, 14-hydro-15-hydroxy ajugapitin, beta-sitosterol, and stigmasterol. The structural elucidation was carried out by spectroscopic techniques. 相似文献
958.
The structure of a novel 2,3,4- trisubstituted furanoid lignan, designated sylvone, was established as from detailed spectroscopical and chemical studies. 相似文献
959.
Sandeep Pal Danilo Roccatano Horst Weiss Harald Keller Florian Müller-Plathe 《Chemphyschem》2005,6(8):1641-1649
We present results from molecular dynamics simulations of water near structured hydrophobic surfaces. The surface structures reported herein are a planar alkane crystal as a reference and crystals with a hole and a protrusion of approximately 2.5 nm diameter and 0.5 nm depth or height. All indicators show that surface structuring increases the hydrophobicity: The water density is reduced near the structure elements, and the number of residual contacts between water and the surface decreases by about 40 % with respect to the planar surface. Thermodynamic integration shows that the interfacial energy of the structured surfaces is about 7 mJ m(-2) higher for structured surfaces than for the planar surface. The hydrophobicity increases by a similar amount for the hole and the protrusion geometries compared to the planar surface. 相似文献
960.
Two novel triphenylene-tethered imidazolium salts were synthesized either by the quaternization of 1-methylimidazole with an ω-bromo-substituted triphenylene or by the quaternization of a triphenylene-substituted imidazole with methyl iodide. Their chemical structures were determined by 1H NMR, 13C NMR, IR, UV spectroscopy and elemental analysis. The thermotropic liquid crystalline properties of these salts were investigated by polarizing optical microscopy and differential scanning calorimetry. These triphenylene-based imidazolium salts with bromide or iodide as counterion show columnar mesophase properties over a wide temperature range. 相似文献