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941.
Preparation of conductive polypyrrole (PPy) composites under supercritical carbon dioxide conditions
Electrically conductive composites were prepared via the chemical oxidative polymerization of the pyrrole monomer in polystyrene
(PS) and zinc neutralized sulfonated polystyrene (Zn-SPS) films under supercritical carbon dioxide (SC-CO2) conditions. The strong swelling effect of SC-CO2 made polypyrrole (PPy) particles not only form on the surface, but also become incorporated into the film, resulting in a
homogeneous structure with a relatively higher conductivity. By comparison, the composite prepared in aqueous solutions shows
a skin-core structure and a conductivity of 3 to 4 orders of magnitude lower than that of the former due to the diffusion-controlled
process of the pyrrole monomer. The percolation thresholds of PS/PPy and Zn-SPS/PPy composites were 6.2% and 2.7% of the volume
fraction of PPy, respectively, much lower than the theoretically predicted value of 16%. Moreover, the conductive composites
prepared under SC-CO2 conditions showed higher thermal stability, especially in the high-temperature region.
Translated from Chemical Journal of Chinese Universities, 2006, 27(4): 771–774 (in Chinese) 相似文献
942.
The conformers of the monohalocyclohexasilanes, Si6H11X (X=F, Cl, Br or I) and the haloundecamethylcyclohexasilanes, Si6Me11X (X=F, Cl, Br or I) are investigated by DFT calculations employing the B3LYP density functional and 6‐31+G* basis sets for elements up to the third row, and SDD basis sets for heavier elements. Five minima are found for Si6H11X—the axial and equatorial chair conformers, with the substituent X either in an axial or equatorial position—and another three twisted structures. The equatorial chair conformer is the global minimum for the X=Cl, Br and I, the axial chair for X=F. The barrier for the ring inversion is ~13 kJ mol?1 for all four compounds. Five minima closely related to those of Si6H11X are found for Si6Me11X. Again, the equatorial chair is the global minimum for X=Cl, Br and I, and the axial chair for X=F. Additionally, two symmetrical boat conformers are found as local minima on the potential energy surfaces for X=F, Cl and Br, but not for X=I. The barrier for the ring inversion is ~14–16 kJ mol?1 for all compounds. The conformational equilibria for Si6Me11X in toluene solution are investigated using temperature dependent Raman spectroscopy. The wavenumber range of the stretching vibrations of the heavy atoms X and Si from 270–370 cm?1 is analyzed. Using the van′t Hoff relationship, the enthalpy differences between axial and equatorial chair conformers (Hax?Heq.) are 1.1 kJ mol?1 for X=F, and 1.8 to 2.8 kJ mol?1 for X=Cl, Br and I. Due to rapid interconversion, only a single Raman band originating from the “averaged” twist and boat conformers could be observed. Generally, reasonable agreement between the calculated relative energies and the experimentally determined values is found. 相似文献
943.
Potentiometric stripping analysis for tin with a gold film electrode formed in situ on glassy carbon
A gold film electrode formed in situ on glassy carbon is used as the working electrode for the determination of tin over the range 0.1–10 μg ml?1. Gold(III) added to the solution provides the film and serves as the oxidant for stripping. Two stripping curves corresponding to Sn(Au) → Sn(II) and Sn(II) → Sn(IV) were observed; either can be used for determinations of tin. The equations for the transition time (i.e., stripping signal) and stripping curve derived were verified experimentally. 相似文献
944.
掺杂阴离子对电化学合成的聚邻甲苯胺性质的影响 总被引:3,自引:0,他引:3
邻甲苯胺在酸性介质中的聚合速率与酸的种类有关,聚合速率影响了各种掺杂阴离子聚合物膜的形态,聚合物的电导率、循环伏安曲线形状受掺杂阴离子的影响,其电容量与掺杂阴离子的种类及形态有关,阴离子的种类对电极电位和紫外-可见光谱无影响。 相似文献
945.
Yoshida N Ishizuka T Yofu K Murakami M Miyasaki H Okada T Nagata Y Itaya A Cho HS Kim D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2854-2866
A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions. 相似文献
946.
Determination of Glimepiride in Human Plasma by LC-MS-MS and Comparison of Sample Preparation Methods for Glimepiride 总被引:1,自引:0,他引:1
Hohyun Kim Kyu Young Chang Chang Hun Park Moon Sun Jang Jung-Ae Lee Hee Joo Lee Kyung Ryul Lee 《Chromatographia》2004,60(1-2):93-98
A sensitive and selective method for quantitation of glimepiride in human plasma was established using liquid chromatography-electrospray ionization tandem mass spectrometry. Three different methods for the sample preparation of glimepiride and an internal standard were investigated (liquid-liquid extraction, solid-phase extraction and protein precipitation). Glipizide was used as an internal standard. Compounds were separated on a C18 column with 80% acetonitrile and 20% deionized water (adjusted to pH 3.5 with acetic acid), as mobile phase at a flow rate of 200 L min–1. By use of multiple reaction monitoring mode in MS-MS with liquid-liquid extraction and solid-phase extraction, glimepiride and glipizide were detected without severe interference from the human plasma matrix. Glimepiride produced a protonated precursor ion ([M+H]+) at m/z 491 and a corresponding product ion at m/z 352, and the internal standard produced a protonated precursor ion ([M+H]+) at m/z 446 and a corresponding product ion at m/z 321. The limit of quantitation was 0.1 ng mL–1, 0.5 ng mL–1 and 1.0 ng mL–1 when using liquid-liquid extraction, solid-phase extraction and protein precipitation, respectively. The validation, reproducibility, stability, and recovery of the different sample preparation methods were comparable and all the methods gave reliable results. The method has been successfully applied to pharmacokinetic study of glimepiride in human plasma. 相似文献
947.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
948.
Grant J. Sherborne Avetik G. Gevondian Ignacio Funes-Ardoiz Amit Dahiya Christoph Fricke Prof. Dr. Franziska Schoenebeck 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15673-15678
Selective C –C couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C−BPin, C−SiMe3, C−I, C−Br, C−Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C−Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N2+ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N2+, which requires an alternative photo-redox approach to enable productive couplings. 相似文献
949.
D. Mihrin Dr. P. W. Jakobsen A. Voute Dr. L. Manceron Prof. R. Wugt Larsen 《Chemphyschem》2019,20(23):3238-3244
The high-resolution infrared absorption spectrum of the donor bending fundamental band ν of the homodimer (HCN)2 has been collected by long-path static gas-phase Fourier transform spectroscopy at 207 K employing the highly brilliant 2.75 GeV electron storage ring source at Synchrotron SOLEIL. The rovibrational structure of the ν transition has the typical appearance of a perpendicular type band associated with a Σ–Π transition for a linear polyatomic molecule. The total number of 100 assigned transitions are fitted employing a standard semi-rigid linear molecule Hamiltonian, providing the band origin ν0 of 779.05182(50) cm−1 together with spectroscopic parameters for the degenerate excited state. This band origin, blue-shifted by 67.15 cm−1 relative to the HCN monomer, provides the final significant contribution to the change of intra-molecular vibrational zero-point energy upon HCN dimerization. The combination with the vibrational zero-point energy contribution determined recently for the class of large-amplitude inter-molecular fundamental transitions then enables a complete determination of the total change of vibrational zero-point energy of 3.35±0.30 kJ mol−1. The new spectroscopic findings together with previously reported benchmark CCSDT(Q)/CBS electronic energies [Hoobler et al. ChemPhysChem. 19 , 3257–3265 (2018)] provide the best semi-experimental estimate of 16.48±0.30 kJ mol−1 for the dissociation energy D0 of this prototypical homodimer. 相似文献
950.
A sensitive and selective method using liquid chromatography with electrospray ionization mass spectrometric detection was
developed for the quantification of bilobalide and ginkgolides in canine plasma. The analytes were extracted with diethyl
ether-dichloromethane-isopropanol (6:3:1, v/v) after spiking the samples with daidzein (internal standard). The lower limit
of quantification (LLOQ) of the method was 2.5 μg L−1 for ginkgolide B and 10.0 μg L−1 for bilabolide, ginkgolide A and ginkgolide C. The accuracy of the method was within 15% of the actual values over a wide
range of plasma concentrations. The intra-day and inter-day precision was better than 15% (R.S.D.). Finally, the LC-ESI-MS
method was successfully applied to study the pharmacokinetics of ginkgolides and bilabolide after administration of Ginkgo biloba extracts to dogs. 相似文献