全文获取类型
收费全文 | 2548篇 |
免费 | 147篇 |
国内免费 | 189篇 |
专业分类
化学 | 1932篇 |
晶体学 | 27篇 |
力学 | 184篇 |
综合类 | 24篇 |
数学 | 205篇 |
物理学 | 512篇 |
出版年
2024年 | 3篇 |
2023年 | 32篇 |
2022年 | 146篇 |
2021年 | 108篇 |
2020年 | 106篇 |
2019年 | 90篇 |
2018年 | 93篇 |
2017年 | 101篇 |
2016年 | 104篇 |
2015年 | 75篇 |
2014年 | 86篇 |
2013年 | 171篇 |
2012年 | 157篇 |
2011年 | 130篇 |
2010年 | 88篇 |
2009年 | 113篇 |
2008年 | 155篇 |
2007年 | 171篇 |
2006年 | 166篇 |
2005年 | 113篇 |
2004年 | 103篇 |
2003年 | 65篇 |
2002年 | 61篇 |
2001年 | 51篇 |
2000年 | 49篇 |
1999年 | 41篇 |
1998年 | 37篇 |
1997年 | 34篇 |
1996年 | 28篇 |
1995年 | 35篇 |
1994年 | 24篇 |
1993年 | 29篇 |
1992年 | 33篇 |
1991年 | 18篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 9篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1976年 | 3篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1962年 | 1篇 |
排序方式: 共有2884条查询结果,搜索用时 0 毫秒
31.
A conductance study concerning the association of Na+, K+, Rb+, and Cs+ with 1,13-dibenzo-24-crown-8 in acetonitrile has been carried out at 35, 30, 25, 20, and 15°C. The observed molar conductivities were found to decrease significantly for mole ratios less than unity. A model involving 11 stoichiometry has been used to analyze the conductivity data. The stability constant, K, and the molar conductivity C for each 11 complex were determined from the conductivity data by using a nonlinear least squares curve fitting procedure. The binding sequence, based on the value of log K at 25°C, is found to be Rb+>Cs+>K+>Na+. Values of Ho and So are reported and their significance is discussed. 相似文献
32.
Preparation and characterization of Mg(II)-, Ca(II) and Cd(II) complexes of 1,2-ethanediol and water
Mixed ligand complexes of different compositions were prepared with water, sulfate ion and 1,2-ethanediol as ligand. IR spectra and the thermoanalytical curves of the complexes were recorded. Oxygen atoms bound by one or two coordinate bonds to the metal ion, or by hydrogen-bonds in the crystal, were observed. As for the water molecule, 1,2-ethanediol molecules of crystal and monohydrate type were found, depending on the type of binding of the oxygen atoms.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
33.
34.
Soosai Devaraj 《Tetrahedron letters》2007,48(17):3077-3081
Novel colorimetric receptors 1-[(2-hydroxy-5-bromo-benzylidene)-amino]-anthraquinone, 1-[(2-hydroxy-5-methyl-benzylidene)-amino]-anthraquinone, and 1-[(2-hydroxy-5-nitro-benzylidene)-amino]-anthraquinone have been synthesized as fluoride ion sensors. A color change was observed visually (naked-eye) upon addition of fluoride ions in organic solvents to solutions of the receptors. 相似文献
35.
Susan Robertson David Ellis Georgina M. Rosair Alan J. Welch 《Journal of organometallic chemistry》2003,680(1-2):286-293
The reaction of the labelled carborane ligand [3-Et-7,8-Ph2-7,8-nido-C2B9H8]2− with a source of {Pt(PMe2Ph)2}2+ affords non-isomerised 1,2-Ph2-3,3-(PMe2Ph)2-6-Et-3,1,2-closo-PtC2B9H8 (1). The analogous reaction between [3-F-7,8-Ph2-7,8-nido-C2B9H8]2− and {Pt(PMe2Ph)2}2+ yields 1,8-Ph2-2,2-(PMe2Ph)2-4-F-2,1,8-closo-PtC2B9H8 (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph2-2,2-(PMe2Ph)2-4-Et-2,1,8-closo-PtC2B9H8 (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB2 face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques. 相似文献
36.
The high TC
superconducting phase Bi2Sr2Ca2Cu3Ox
(2223) in the Pb-BSCCO system has been produced by EDTA-gel processing
using nitrate solutions. The precursor has heated in two stages, at 300 and
800°C each for 2 h, to avoid the burning of the important species involved
in the final product. The effects of time (6 to 48 h) and temperature (845
and 855°C) on the formation of the 2223 phase have been studied by sintering
the samples in air. Thermal analysis (TG/DTA), X-ray diffraction (XRD), scanning
electron microscopy (SEM) and a vibrating sample magnetometer (VSM) have been
employed to investigate the powder produced at different stages of decomposition,
oxidation and formation of sintered materials from the powders. The volume-fraction
of the 2223 phase at 845°C increases with time, the maximum value of the
2223 phase was obtained at 120 h. It has been observed that the formation
of the high TC phase
is remarkably enhanced at the temperature of the endothermic peak of the DTA
curve. The best result has been obtained in the sample sintered for 24 h at
the temperature 855°C (endothermic peak). This also indicated that at
855°C, the large volume-fraction of 2223 phase with TC
113 K grew in short time and as the sintering time increased, it decomposed
into the Bi2Sr2CaCu2Ox
(2212) phase and other phases. 相似文献
37.
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
38.
A sensitive and convenient high-performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) assay is described for the (5-HT(lB/lD)) receptor agonist sumatriptan in human plasma. Sumatriptan was recovered from plasma (81.8 +/- 6.8%) by liquid-liquid extraction. The mobile phase flow rate was 0.3 mL/min and consisted of methanol:water:formic acid (90:10:0.1, v/v/v). The analytical column (4.6 x 100 mm) was packed with Partisil C(8) (5 micro m). The standard curve was linear from 0.7 to 70.4 ng/mL (r(2) > 0.99). The lower limit of quantitation was 0.7 ng/mL. The assay was specific, accurate (percentage deviation from nominal concentrations were <15%), precise and reproducible (within- and between-day coefficients of variation <10.3%). Sumatriptan in plasma was stable over three freeze/thaw cycles and at room temperature for one day. The utility of the assay was demonstrated by following sumatriptan plasma concentrations in two healthy subjects for 8-12 h following a single 20 mg intranasal dose. 相似文献
39.
Summary A new equation is derived relating the retention index to the molecular polarizabilities, ionization potentials and permanent dipole moments of the stationary phase and the solute.Various implications of this equation to quantitative structure-retention relationships are discussed. 相似文献
40.
The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed. 相似文献