全文获取类型
收费全文 | 38330篇 |
免费 | 6400篇 |
国内免费 | 4328篇 |
专业分类
化学 | 26159篇 |
晶体学 | 520篇 |
力学 | 2469篇 |
综合类 | 285篇 |
数学 | 4428篇 |
物理学 | 15197篇 |
出版年
2024年 | 143篇 |
2023年 | 777篇 |
2022年 | 1286篇 |
2021年 | 1368篇 |
2020年 | 1487篇 |
2019年 | 1415篇 |
2018年 | 1256篇 |
2017年 | 1177篇 |
2016年 | 1777篇 |
2015年 | 1762篇 |
2014年 | 2140篇 |
2013年 | 2693篇 |
2012年 | 3268篇 |
2011年 | 3399篇 |
2010年 | 2327篇 |
2009年 | 2290篇 |
2008年 | 2488篇 |
2007年 | 2236篇 |
2006年 | 2137篇 |
2005年 | 1650篇 |
2004年 | 1328篇 |
2003年 | 1120篇 |
2002年 | 1038篇 |
2001年 | 832篇 |
2000年 | 870篇 |
1999年 | 821篇 |
1998年 | 731篇 |
1997年 | 683篇 |
1996年 | 691篇 |
1995年 | 616篇 |
1994年 | 541篇 |
1993年 | 430篇 |
1992年 | 425篇 |
1991年 | 330篇 |
1990年 | 302篇 |
1989年 | 239篇 |
1988年 | 204篇 |
1987年 | 172篇 |
1986年 | 153篇 |
1985年 | 152篇 |
1984年 | 104篇 |
1983年 | 71篇 |
1982年 | 60篇 |
1981年 | 36篇 |
1980年 | 16篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 1篇 |
1959年 | 1篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
The flow-injection system combines on-line ion-exchange preconcentration with atomic absorption spectrometry (a.a.s.) for the determination of traces (μg l?1) of heavy metals in water samples. Miniature columns packed with 60–100 mesh chelating resin (122) with a salicylic acid functional group are used for preconcentration. A multifunctional rotary sampling valve which incorporated two parallel sampling columns allows sampling, exchange, elution and a.a.s. to be achieved sequentially. The increases in sensitivity for nickel, copper, lead and cadmium were 20–28-fold at a sampling rate of 40 h?1 with 5-ml samples. Relative standard deviations were 1.5–4.1%. The recoveries of these four metals added to tap, sea and polluted waters were generally satisfactory, except for cadmium in polluted water. The effects of column diameter and elution flow rates on sensitivity are discussed. Possible interferences are described. 相似文献
72.
Xu X Zhao J Jiang D Kong J Liu B Deng J 《Analytical and bioanalytical chemistry》2002,374(7-8):1261-1266
A novel hydrogen peroxide biosensor was developed based on the immobilization of horseradish peroxidase (HRP) in a TiO(2) sol-gel matrix on an electropolymerized phenazine methosulfate (PMS) modified electrode surface. Such membranes are of interest due to their high surface area, biological compatibility, and ease of fabrication. HRP entrapped in the TiO(2) matix was stable and retained its activity to a large extent. Cyclic voltammetry and amperometric measurements were employed to demonstrate the feasibility of electron transfer between immobilized HRP and the glassy carbon electrode via electropolymerized PMS. The influence of various experimental parameters such as operating potential, pH, temperature, and stability was investigated for optimum analytical performance. The biosensor provided a wide linear calibration range from 4.0x10(-6) M to 1.0x10(-3) M, with a detection limit of 8.0x10(-7) M at a signal-to-noise ratio of 3. The sensor retained 80% of its original activity after two months of operation. 相似文献
73.
The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence. 相似文献
74.
Xiao Wen Hu Zhi Min Zheng Cai Hong Xu 《中国化学快报》2007,18(11):1351-1352
Three new 1,3-bis(phenylethynyl)disilazanes were synthesized from the reaction of 1,3-dichlorodisilazanes with (phenylethy- nyl)lithium,and characterized by infrared (IR) spectra,nuclear magnetic resonance (NMR) and mass spectrometry (MS). 相似文献
75.
76.
Protein-ligand interactions may lead to the formation of multiple molecular complexes in dynamic exchange, affecting the kinetic and thermodynamic characteristics of the binding equilibrium. We followed the dissociation kinetics of the transient and specific complex of an antithrombotic peptide N-acetyl-Asp(55)-Phe-Glu-Glu-Ile-Pro(60)-Glu-Glu-Tyr-Leu-Gln(65) with human prothrombin by use of (15)N NMR relaxation dispersion spectroscopy of the peptide. Every one of the five (15)N-labeled adjacent residues of the peptide exhibited apparently different kinetic exchange and relaxation behaviors, which were especially evident at different concentrations of prothrombin. Binding-induced (15)N relaxation dispersion of residues Phe(56), Glu(57), Glu(58), and Ile(59) can be fitted phenomenologically to a two-site on-and-off exchange mechanism with physically feasible relaxation and kinetic parameters obtained for residues Phe(56), Glu(58), and Ile(59), independent of the prothrombin concentration. The apparent kinetic parameters of Glu(57) show some dependence on the concentration of prothrombin and the extracted transverse relaxation rate for Glu(57) in the bound state was severalfold higher than that expected for a protein-peptide complex with a size of approximately 72 kDa. In addition, the equilibrium population of the bound peptide obtained for Glu(57) was inconsistent with those for Phe(56), Glu(58), and Ile(59) and with the prothrombin/peptide ratios used in the experiments. These discrepancies can be explained by the presence of two conformations for the peptide-protein complex exchanging at a rate of approximately 100 s(-)(1). In all, our study shows that fast dissociation of protein-peptide complexes can be studied quantitatively using peptide (15)N NMR relaxation dispersion measurements without a precise knowledge of the peptide and protein concentrations. In addition, protein titration was found to improve the accuracy of quantitative analysis and may make it possible to determine the rate of conformational changes within the protein-peptide complex. 相似文献
77.
We developed a novel on-line preconcentration procedure for microchip gel electrophoresis (MCGE), which enables application of electrokinetic supercharging (EKS) for highly sensitive detection of DNA fragments on a cross-geometry microchip. In comparison with conventional pinched injection using the cross microchip, the present approach allows loading a much larger amount of the sample by taking advantage of a newly developed operational mode. In order to obtain high preconcentration effect and prevent splitting of an enriched sample into subchannels, i.e., off the detector range, effects of the voltage applied on the reservoirs and the time of isotachophoretic preconcentration were examined. The optimal balance between the voltage and time was found for a high-sensitivity analysis of DNA fragments. After experimental optimization the detection limit of a 150 bp fragment was as low as 0.22 mg/L (S/N = 3) that is 10 times better than using the conventional pinched injection. 相似文献
78.
79.
80.