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51.
    
Current carbon and sulphur isotope ratios (δ13C and δ34S) suggest there were major shifts in partitioning between reduced and oxidised reservoirs of carbon and sulphur during the Early Cretaceous. However, the δ13C and δ34S records are composed from different Ocean Drilling Program sites and are hard to correlate at high resolution. We present high-resolution Aptian δ13Corg and δ34Sbarite values derived from the same set of samples, enabling a higher certainty correlation than previously possible. Two major hypotheses aim to explain the Early Aptian S-isotope excursion: increased volcanic degassing and/or fluctuations in the marine sulphate concentration. Our S-isotope data provide tight constraints on the timing and magnitude of volcanic flux required. We show that the observed S-isotope signature can be explained by a 2 Ma pulse of increased volcanic flux, injecting ∼4.5×1018 mol C into the atmosphere. Further work is needed to evaluate whether these fluxes are compatible with the existing C-isotope record.  相似文献   
52.
    
Sources and processes affecting the sulphur cycle in the Canyon Creek watershed in Alberta (Canada) were investigated. The catchment is important for water supply and recreational activities and is also a source of oil and natural gas. Water was collected from 10 locations along an 8 km stretch of Canyon Creek including three so-called sulphur pools, followed by the chemical and isotopic analyses on water and its major dissolved species. The δ2H and δ18O values of the water plotted near the regional meteoric water line, indicating a meteoric origin of the water and no contribution from deeper formation waters. Calcium, magnesium and bicarbonate were the dominant ions in the upstream portion of the watershed, whereas sulphate was the dominant anion in the water from the three sulphur pools. The isotopic composition of sulphate (δ34S and δ18O) revealed three major sulphate sources with distinct isotopic compositions throughout the catchment: (1) a combination of sulphate from soils and sulphide oxidation in the bedrock in the upper reaches of Canyon Creek; (2) sulphide oxidation in pyrite-rich shales in the lower reaches of Canyon Creek and (3) dissolution of Devonian anhydrite constituting the major sulphate source for the three sulphur pools in the central portion of the watershed. The presence of H2S in the sulphur pools with δ34S values ∼30 ‰ lower than those of sulphate further indicated the occurrence of bacterial (dissimilatory) sulphate reduction. This case study reveals that δ34S values of surface water systems can vary by more than 20 ‰ over short geographic distances and that isotope analyses are an effective tool to identify sources and processes that govern the sulphur cycle in watersheds.  相似文献   
53.
    
ABSTRACT

Freshwater bivalve shell oxygen isotope values (δ18OS) may act as a recorder of river δ18O variations that can then be interpreted in terms of hydrology (e.g. precipitation–evaporation balance, precipitation and river discharge patterns). We investigated the potential of this proxy measured across the hinge of South American unionid shells: Anodontites elongatus collected in Peru and A. trapesialis in Brazil. The isotopic signatures were reproducible between individuals of the same species. A. trapesialis clearly showed a strong δ18OS cyclicity in accordance with its growth patterns while A. elongatus presented less clear δ18OS with lower amplitude. We confirm that the deposition of successive growth lines and increments is annual, with growth line corresponding to the wet season. Also, we suggest that low amplitude of δ18OS in the A. elongatus shells indicates a habitat close to the river while large amplitude of δ18OS cycles observed in A. trapesialis shells would reflect a floodplain lake habitat, seasonally disconnected from the river and thus subjected to higher seasonal fluctuations in water δ18O. Considering these promising first results, future studies could be directed towards the use of fossil shells to reconstruct the past and present hydrological and geochemical conditions of the Amazon.  相似文献   
54.
本文考虑了平行机实时到达的在线问题,模型中,工件是陆续到达的,工件的个数,到达时间是事先未知的,而且只有当工件到达,才知其加工时间,目标是使所有工件都加工完成的时间达到最小。  相似文献   
55.
Heats of formation of rate-earth monosulfate complexes have been measured calorimetrically for the ions La3+, Sm3+, Tb3+, and Er3+, in D2O and H2O solvents. Within the limits of experimental error there is no evidence for a solvent isotope effect on the heat and entropy changes of these complexation reactions.This paper was abstracted from W.D.W.'s Ph.D. dissertation, May 1973.  相似文献   
56.
A potentiometric method using a glass electrode has been applied to determination of ionization constants for deuterium oxide (D2O) in binary mixtures of D2O with dioxane, tetrahydrofuran, acetone, dimethylsulfoxide, CH3CH2OD, and CH3OD at 25°C. The results are compared with values of ionization constants for H2O obtained previously in the corresponding H2O-organic mixtures, and the isotope effect is shown to be small. Further calculations with the D2O results show that the first five solvents mentioned above are neither appreciably acidic nor basic in D2O solution, but that CH3OD shows slightly acidic behavior (pKa=16.0±0.3).  相似文献   
57.
The D/H ratios of hydrogen gas in equilibrium with aqueous sodium chloride solutions of 2, 4 and 6 molalities were determined within the range 10 to 95°C, using a hydrophobic platinum catalyst. With each of the different sodium chloride concentrations, the hydrogen isotope effect between the solution and pure water changes linearly with the square of the reciprocal temperature. On the basis of the results for hydrogen isotope fractionation observed in this study, and those of hydrogen isotope fractionation between pure water and vapor, it is concluded that the structure of the aqueous sodium chloride solution does not change significantly with temperature. The hydrogen isotope effect is evidently different from the results of vapor pressure isotope effects (VPIE) on sodium chloride solutions measured on separated isotopes. The difference between the present work and the VPIE studies is probably due to a non-ideal behavior in a mixture of isotopic water molecules and/or to a H2O-D2O disproportionation reaction in sodium chloride solutions. The distinction between the latter two mechanisms can not be differentiated at present.  相似文献   
58.
    
Radiolabelling is fundamental in drug discovery and development as it is mandatory for preclinical ADME studies and late-stage human clinical trials. Herein, a general, effective, and easy to implement method for the multiple site incorporation of deuterium and tritium atoms using the commercially available and air-stable iridium precatalyst [Ir(COD)(OMe)]2 is described. A large scope of pharmaceutically relevant substructures can be labelled using this method including pyridine, pyrazine, indole, carbazole, aniline, oxa-/thia-zoles, thiophene, but also electron-rich phenyl groups. The high functional group tolerance of the reaction is highlighted by the labelling of a wide range of complex pharmaceuticals, containing notably halogen or sulfur atoms and nitrile groups. The multiple site hydrogen isotope incorporation has been explained by the in situ formation of complementary catalytically active species: monometallic iridium complexes and iridium nanoparticles.  相似文献   
59.
    
Lithium-ion batteries have been developing intensively and earn an unprecedented reputation, yet advanced performance and safety issue still require considerable investigation. Separator is vital to comprehensive properties of batteries, where the mechanical properties are key to breaking through of new-type separator. Unfortunately, electrolyte submersion has caused damage to strength of cellulose separator. Whereupon, in this work, cellulose separator is optimized by introducing lignin particles to promote electrolyte-immersed mechanical strength. Experiments are conducted concerning surface morphology, contact angle, porosity, electrolyte uptake, mechanical properties and electrochemical performance. Molecular simulation is implemented to explore the mechanism of tensile behavior of cellulose and lignin subjected to electrolyte solvents. Experimental results confirm positive effect of lignin addition in improving mechanical properties and simultaneously maintaining impressive electrochemical performance of the cellulose/lignin composites separators. Besides, lignin addition amount of 2.5% and 5% is recommended to achieve promising overall properties. Molecular simulation has successfully unveiled that weakening of cellulose separator submerged in electrolyte is resulted by the deformed cellulose amorphous region and the promoting effect of adding lignin is contributed from the new hydrogen bonds generated between cellulose and lignin molecules. Hopefully, this work provides novel insight on preparing remarkable separator and mechanism of materials behavior.  相似文献   
60.
Thermodynamic and kinetic parameters have been established for the reaction between the carbon acid, 4-nitrophenylnitromethane, (4-NPNM), and the base N’-n-propyl-N,N-di-n-propylbenzimidamide, (N’PDPBA), in mesitylene and in chlorobenzene. In some cases deuteron transfer from 4-(D2)NPNM to the base has also been studied. In addition, some results for the proton transfer reaction in tetrahydrofuran have been collected. Spectrophotometric methods have been employed to monitor the ion-pair product, which is solvatochromic. In general the solvent dependence of the parameters is as expected, but there is some indication of specific solvation. The kinetic isotope effects of 11 and 8 in mesitylene and chlorobenzene, respectively, are larger than those predicted classically. However, as is discussed the n-propyl group on the secondary nitrogen of the base may serve to reduce the extent of tunneling compared to that in an unsubstituted analogue by a steric effect.  相似文献   
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