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91.
The first investigation on catalytic asymmetric [2, 3]-sigmatrop-ic rearrangement of sulfur ylides generated from carbenoids andallenic phenyl sulfide was carried out. Up to 55% ee value wasobtained. 相似文献
92.
The sintering and the structure of clinkers, modified by the introduction of different ionic forms of sulfur and phosphorus
into the raw mix, were examined. One reference synthetic mixture and 25 modified mixtures were prepared by mixing the reference
sample with 0.5, 1.0, 1.5, 2.0 and 2.5%w/w of chemical grade CaSO4, CaS, Ca3(PO4)2, CaHPO4 and Ca(H2PO4)2. Free lime content in all samples was measured. The sintering reactions in samples were recorded by means of differential
thermal analysis. The texture of the clinkers was examined using a scanning electron microscope and EDX. It is concluded that,
despite of their relatively low doping concentration in the raw mix, P and S affect considerably its reactivity and the texture
of the clinker. The various ionic forms of the same element (SO4
2-, S2- for S, PO4
3-, HPO4
2- and H2PO4
- for P) exhibit a different and unequivocal effect on the reactivity of the synthetic raw mix and on the texture of the corresponding
clinkers. S (in both forms) and P (added as HPO4
2-) are mainly dissolved in the melt and they have a positive effect on the burnability of the raw mix. P (added as PO4
3- or H2PO4-) is preferentially accumulated in belite. In this case further stabilization of β-C2S occurs and the binding of the free lime is hindered.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
93.
Bradley D. Fahlman Andrew D. Daniels Gustavo E. Scuseria Andrew R. Barron 《Journal of Cluster Science》2002,13(4):587-599
Thermodynamic and mechanistic features of the chalcogen exchange reaction between [RGa(
3-Te)]4 and elemental sulfur or selenium have been studied employing density functional theory (DFT) calculations using the BL3YP basis set and Stuttgart pseudopotentials. For [MeGa(
3-E)]4 (E=S, Se, Te) the correlation between the calculated parameters and diffraction data for their isolable analogs is greater than 98%. Each step of the conversion of [MeGa(
3-Te)]4 to [MeGa(
3-E)]4 via [Me4Ga4(
3-Te)4–x
(
3-E)
x
] (E=S, Se) is predicted to occur as a series of isolated reactions. The entropy change for each chalcogen exchange is small in magnitude and corresponds to the degree of cage distortion within the cubane molecules. Calculations performed on [MeGa(
3-Te)]4...S8 and [MeGa(
3-Te)]4-S suggest that an increase in electrophilicity of the gallium next to a surface bound tellurium may result in nucleophilic cage opening for which intermediate structures are calculated. 相似文献
94.
Analysis of the NMR spectra of 1,2,3-trichloropropane and 1,2,3-tribromopropane in various media shows the most stable conformer to be AG-. The populations of several conformera have been estimated by using pure trans and gauche coupling constants obtained from closely similar molecules. The calculated populations found in non-polar solvents agree well with those obtained by electron diffraction studies in the gas phase. It is suggested that the AG- form is stabilised relative to AG+ by the former having two parallel (1:3) halogen-hydrogen attractions against one in the AG+ form. Comparison is made to related molecules where the most stable conformers also have the greatest number of parallel (1:3) halogen-hydrogen interactions. 相似文献
95.
A novel DBU-assisted carbonylation of amines with carbon monoxide and sulfur has been developed for the synthesis of S-alkyl thiocarbamates. In the presence of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), S-alkyl thiocarbamates are synthesized in excellent yields from amines, carbon monoxide, sulfur, and alkyl halides under mild conditions (1 atm, 20°C). In the absence of DBU, however, no formation of S-alkyl thiocarbamate is observed. The present DBU-assisted carbonylation can also be applied to new synthetic methods for benthiocarb and orthobencarb (herbicides) and carbamoyl chlorides. 相似文献
96.
通过对广义簇合物生长的自调整模型的解析,得出了粒子在均匀几率密度场下簇合物生长形态的变化特征,揭示了表征其生长形态结构分式维数D的物理意义,同时考查了格子模型对簇合物生长形态的影响以及自调整模型的动力学行为。 相似文献
97.
An oxidation method (sulfone method) for the determination of polycyclic aromatic sulfur heterocycles (PASH) in diesel fuel is presented. The aromatic fraction of a diesel fuel, isolated by solid phase extraction, is oxidized under controlled conditions with hydrogen peroxide. The oxidation products, mainly methylated dibenzosulfone, are determined and quantified directly, without further clean-up, by HPLC with photodiode-array detection. 相似文献
98.
Antifouling coatings are the most reliable way to prevent biofouling of immersed surfaces. As concerning the high toxicity of organotin paints, the tendency is the development of coatings, which do not present environmental risks. In this work, we prepare binders from modification of acrylic copolymers containing free carboxylic acid groups. Biocides chosen are tertiary ammonium salts; alkyl chain substituents with different length are considered. The chemical modifications of resins are carried out via a single step reaction. Modification extents are monitored through proton nuclear magnetic resonance and thermogravimetric analysis and the modified resins are characterised by Fourier transform infrared spectroscopy. The glass transition temperature of the acrylate systems is assessed by dynamical mechanical analysis (pin point method) and compared with data obtained by differential scanning calorimetry. The erosion and antifouling properties of the binders are followed during an exposure to marine environment by a visual observation. 相似文献
99.
The hypothesis of the classical chemistry about bond dipoles resulting from shifts of separate pairs of electrons is proved using the non-canonical method of molecular orbitals (MOs). To this end, a relation is sought between the total charge distribution inside an individual chemical bond of a polyatomic molecule and the square of the respective single localized MO (LMO). General expressions for these MOs are obtained directly on the basis of the Brillouin theorem without invoking additional localization criteria. The two characteristics under comparison are presented in an explicit algebraic form in terms of meaningful components. Reshaping of square of the ‘own’ LMO of the given bond is shown to play the decisive role in the formation of secondary dipoles of initially homopolar bonds (e.g. of C–C and C–H bonds in substituted alkanes), as well as of bonds of relatively low initial polarity. Thus, representability of these dipoles by shifts of the ‘own’ pairs of electrons of respective bonds is supported. For bonds of a high initial polarity, the secondary dipoles are shown to originate mainly from contributions of LMOs of other bonds extending over the antibonding basis orbital of the given bond. Moreover, the actual secondary bond dipole takes an opposite direction vs. that predicted by the shift of the respective ‘own’ pair of electrons in this case. The latter result serves to account for the known low nucleofugality of highly electronegative heteroatoms in the SN2 reactions. 相似文献
100.
煤的超临界醇萃取脱硫:Ⅲ.形态硫的变化 总被引:1,自引:0,他引:1
本文分别应用Mossbauer谱和XPS(X射线光电子能谱)技术考察不同反应 条件下固体产物中的无机硫和有机硫的形态变化,结果表明;在超临界醇萃取脱硫过程中,黄铁矿硫的转化反应如下:FeS2-FeS+Fe1-xS,,转化的数量和深度主要取决于反应温度。275℃时磁黄铁矿(Fe1-xS)形式为FeS1.101,450℃时为FeS1.085;有机硫基团中PhSH ,Ph2S和四氢噻吩较易脱除,Ph2S 相似文献