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991.
By means of cyclic voltammetry (CV) and DFT calculations, it was found that the electron-acceptor ability of 2,1,3-benzochalcogenadiazoles 1 – 3 (chalcogen: S, Se, and Te, respectively) increases with increasing atomic number of the chalcogen. This trend is nontrivial, since it contradicts the electronegativity and atomic electron affinity of the chalcogens. In contrast to radical anions (RAs) [ 1 ].− and [ 2 ].−, RA [ 3 ].− was not detected by EPR spectroscopy under CV conditions. Chemical reduction of 1 – 3 was performed and new thermally stable RA salts [K(THF)]+[ 2 ].− ( 8 ) and [K(18-crown-6)]+[ 2 ].− ( 9 ) were isolated in addition to known salt [K(THF)]+[ 1 ].− ( 7 ). On contact with air, RAs [ 1 ].− and [ 2 ].− underwent fast decomposition in solution with the formation of anions [ECN], which were isolated in the form of salts [K(18-crown-6)]+[ECN] ( 10 , E=S; 11 , E=Se). In the case of 3 , RA [ 3 ].− was detected by EPR spectroscopy as the first representative of tellurium–nitrogen π-heterocyclic RAs but not isolated. Instead, salt [K(18-crown-6)]+2[ 3 -Te2]2− ( 12 ) featuring a new anionic complex with coordinate Te−Te bond was obtained. On contact with air, salt 12 transformed into salt [K(18-crown-6)]+2[ 3 -Te4- 3 ]2− ( 13 ) containing an anionic complex with two coordinate Te−Te bonds. The structures of 8 – 13 were confirmed by XRD, and the nature of the Te−Te coordinate bond in [ 3 -Te2]2− and [ 3 -Te4- 3 ]2− was studied by DFT calculations and QTAIM analysis.  相似文献   
992.
As the spacer length in 1,2-dimethylimidazolium-based dications increases beyond a specific point (six methylene units), they fail in structure-directing towards STW zeolites in any synthetic conditions. These dications can instead produce, under fluoride concentrated conditions, either *BEA [in the case of the eight-methylene-unit structure-directing agent (SDA)] or MWW (ten methylene units) zeolites. For any length of the dication, the default zeolite (MTW) is a relatively dense zeolite containing a unidimensional channel, whereas the zeolite demanding most specificity (STW, *BEA or MWW) is more porous, affording a larger concentration of the dication to be occluded. This work provides the first reported fluoride synthesis of pure silica MWW zeolites. Charge balance of the organic dications in this zeolite was achieved by combining “structural” silanolates, regular “connectivity defects” and occluded fluoride. Molecular mechanics calculations showed a perfect fit of the decamethylenebis(dimethylimidazolium) dication in the sinusoidal intralayer pore system of MWW. The calculations showed also that the dication is able to stabilize the interlayer space without disturbing the hydrogen-bonding system that holds the layers together in the as-made material. The 19F magic-angle spinning (MAS) NMR presented two distinct resonances at −71 and −83 ppm, which, on the basis of DFT calculations, we tentatively assigned to fluoride occluded in [4662] and [415262] cages of the MWW structure, respectively. The same DFT study determines a different chemical shift of one methyl 13C nuclear magnetic resonance according to the imidazolium ring residing in the sinusoidal channels or in the large cup cavities, thus explaining an experimentally observed splitting of that resonance.  相似文献   
993.
In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.  相似文献   
994.
Herein we summarized some clean preparation examples to emphasize the concept of dual roles design (or named as “two birds one stone strategy”) in green and sustainable chemistry. In those examples, the reactants and/or solvent play dual roles rendering a cleaner organic preparation process. Consequently, both the chemical waste and manufacturing cost could be reduced.  相似文献   
995.
Hydralazine has been widely employed in the development of drugs, derivatization reagents, and ligands. In the present work, we reported a new type of dehydrogenated ion [M ? H]+ that was produced from the hydralazine derivative of hexanal in electrospray ionization mass spectrometry (ESI‐MS). The formation of [M ? H]+ ions in the ESI‐MS was found to be independent on the mobile phase composition of the liquid chromatography and ESI source parameters. A series of hydralazine derivatives of aldehyde were investigated to confirm this phenomenon. The results showed that hydralazine derivatives of aldehydes that contained an sp3 hybridization carbon with a hydrogen at the α‐position of aldehydes could form the unexpected [M ? H]+ ions, whereas hydralazine derivative of acetone could only generate [M + H]+ ion in the ESI‐MS. We proposed the possible formation mechanism of [M ? H]+ ion for the hydralazine derivatives of aldehydes: the [M ? H]+ ion was possibly formed by the loss a hydrogen molecule (H2) from the protonated ion [M + H]+. The results obtained from density functional theory (DFT) calculations supported this proposed formation mechanism of [M ? H]+ ion.  相似文献   
996.
Increasing the stability of perovskite solar cells is one of the most important tasks in the photovoltaic industry. Thus, the structural, energetic, and electronic properties of pure CH3NH3PbI3 and fully doped compounds (CH3NH3PbBr3 and CH3NH3PbCl3) in cubic and tetragonal phases were investigated using density functional theory calculations. We also considered the effects of mixed halide perovskites CH3NH3PbI2X (where X = Br and Cl) and compared their properties with CH3NH3PbI3. The DFT results indicate that the phase transformation from tetragonal to cubic phase decreases the band gap. The calculated results show that the X‐site ion plays a vital role in the geometrical stability and electronic levels. An increase in the band gap and a reduction in the lattice constants are more apparent in CH3NH3PbI2X compounds (I > Br > Cl).  相似文献   
997.
The joint of the donor and acceptor moieties allows a facile and effective strategy to develop novel organic conjugated materials. However, few pieces of work report the understanding of the donor–acceptor interactions at the molecular level. Herein, we developed three small molecules containing one acceptor motif with different amounts of the donor unit. By combining theoretical calculations and energy level characterization, the lowest unoccupied molecular orbital (LUMO) levels of the three molecules were proven to be almost identical. The molecular packing modes were evaluated from crystal structure prediction. Owing to the donor–acceptor interactions, the packing mode can be tuned from a 1D slipped stacking to a 2D brick layer. The 2D molecular packing and charge transport channel endowed the materials a higher electron mobility of 3.29 cm2 V?1 s?1 in the single‐crystal field‐effect transistors after such modulation.  相似文献   
998.
Isomerism of atomically precise noble metal nanoclusters provides an excellent platform to investigate the structure–property correlations of metal nanomaterials. In this study, we performed density functional theory (DFT) and time‐dependent (TD‐DFT) calculations on two Au21(SR)15 nanoclusters, one with a hexagonal closed packed core (denoted as Au21 hcp ), and the other one with a face‐centered cubic core (denoted as Au21 fcc ). The structural and electronic analysis on the typical Au–Au and Au–S bond distances, bond orders, composition of the frontier orbitals and the origin of optical absorptions shed light on the inherent correlations between these two clusters.  相似文献   
999.
The reactivity of 2-alkylidene-4-oxothiazolidine S-oxides under the Pummerer reaction conditions, using Ac2O, TFAA, SOCl2 and SOBr2 as initiators, has been examined. Almost all reactions proceeded with absolute regioselectivity yielding α-substituted sulfides or vinyl-chloro derivatives. The mechanism for the formation of the latter products was postulated and proved experimentally.  相似文献   
1000.
In the design of dual-imaging probes, the first functionalized and neutral heterobimetallic Re(I)–Gd(III) complex, highly soluble in aqueous solutions, has been prepared. This system exhibits interesting photophysical properties (λem = 578 nm, ? = 1.4%) for optical imaging and substantial higher relaxivity (r1 = 6.6 mM−1 s−1 at 0.47 T and 37 °C) than the clinically used MRI contrast agents. Moreover, this system incorporates an aromatic ester functionality suitable for bioconjugation.  相似文献   
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