全文获取类型
收费全文 | 29086篇 |
免费 | 100篇 |
国内免费 | 271篇 |
专业分类
化学 | 10721篇 |
晶体学 | 263篇 |
力学 | 1379篇 |
综合类 | 12篇 |
数学 | 8989篇 |
物理学 | 8093篇 |
出版年
2022年 | 58篇 |
2021年 | 66篇 |
2020年 | 40篇 |
2019年 | 32篇 |
2018年 | 1206篇 |
2017年 | 1458篇 |
2016年 | 728篇 |
2015年 | 556篇 |
2014年 | 483篇 |
2013年 | 655篇 |
2012年 | 3136篇 |
2011年 | 2314篇 |
2010年 | 1806篇 |
2009年 | 1548篇 |
2008年 | 550篇 |
2007年 | 612篇 |
2006年 | 593篇 |
2005年 | 4438篇 |
2004年 | 3928篇 |
2003年 | 2308篇 |
2002年 | 485篇 |
2001年 | 285篇 |
2000年 | 88篇 |
1999年 | 174篇 |
1998年 | 112篇 |
1997年 | 73篇 |
1996年 | 43篇 |
1995年 | 44篇 |
1994年 | 45篇 |
1992年 | 169篇 |
1991年 | 152篇 |
1990年 | 134篇 |
1989年 | 107篇 |
1988年 | 100篇 |
1987年 | 58篇 |
1986年 | 43篇 |
1985年 | 39篇 |
1984年 | 28篇 |
1983年 | 29篇 |
1979年 | 30篇 |
1976年 | 79篇 |
1975年 | 37篇 |
1974年 | 41篇 |
1973年 | 49篇 |
1972年 | 41篇 |
1970年 | 34篇 |
1969年 | 37篇 |
1968年 | 36篇 |
1967年 | 30篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Sun S Szakal C Winograd N Wucher A 《Journal of the American Society for Mass Spectrometry》2005,16(10):1677-1686
The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations. 相似文献
112.
Shkumbatiuk R Bazel YR Andruch V Török M 《Analytical and bioanalytical chemistry》2005,382(6):1431-1437
A new, simple, rapid, and sensitive spectrophotometric method has been developed for the determination of nitrophenols [picric acid (PA); dinitrophenols (DNP)] in wastewater samples. The method is based on the reaction of nitrophenols with 2-[(E)-2-(4-diethylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3 H-indolium chloride reagent to form the colored ion associates, which are extracted by organic solvents. The molar absorptivity of the ion associates of PA with the investigated reagent ranges from 8.3×104 to 11.3×104 L mol–1 cm–1, depending on the extractant. Because only PA is extracted in an acidic medium with the investigated reagent, but both PA and DNP are extracted in an alkaline medium, it is possible to determine both substances in a mixture. Appropriate reaction conditions have been established. The absorbance of the colored extracts obeys Beers law in the range of 0.04–4.58 mg L–1 PA, 1.0–18.4 mg L–1 2,4-DNP and 1.2–14.7 mg L–1 2,6-DNP, respectively. The limit of detections, calculated from a blank test (n=10; P=0.95), are 0.05 mg L–1 PA, 0.9 mg L–1 (2,4-DNP), and 1.1 mg L–1 (2,6-DNP), respectively. 相似文献
113.
Application of stir bar sorptive extraction for wine analysis 总被引:4,自引:0,他引:4
Yoji?Hayasaka Kevin?MacNamara Gayle?A.?Baldock Randell?L.?Taylor Alan?P.?PollnitzEmail author 《Analytical and bioanalytical chemistry》2003,375(7):948-955
Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used. 相似文献
114.
The application of the recently introduced ethylchloroformate derivatization method for the separation and determination of selenomethionine and selenocystein in selenium-enriched yeast and yeast-free tablets by means of a gas chromatography-mass spectrometry (GC-MS) system has been studied. The efficiency of three methods for the extraction of selenomethionine from the tablets were compared. Total selenium content of the same tablets were measured using inductively coupled plasma (ICP)-MS and it was found that in the selenized yeast tablets about 80% of the total selenium is present as selenomethionine. The results were in agreement with the values in the labels and with the literature. The accuracy of the total selenium analysis was controlled by the analysis of a reference material. 相似文献
115.
This work describes a study of the underpotential deposition (UPD) of Sn2+ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn2+ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, EUPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn2+ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10–7 to 3.64×10–5 M. The method developed here has been applied to determine the tin in a tin plate sample. 相似文献
116.
The development of microplasmas for spectrochemical analysis by optical methods is discussed. Recent achievements in miniaturization are highlighted, especially for three types of plasmas, namely high-frequency plasmas, dc-discharges and microwave plasmas. The potentials of each of these groups of plasmas as sources for atomic emission spectrometry are discussed. Literature citations and experiments indicate that the plasmas are also very useful as atom reservoirs for atomic absorption spectrometry. Methods of sampling, including feeding with gas chromatography effluents, the use of electrothermal vaporization, and the evolution of gaseous species (as shown for the case of Hg vapor), are discussed as prominent interfaces to make use of these sources for elemental analysis. 相似文献
117.
Ballou S Goodpaster J MacCrehan W Reeder D 《Analytical and bioanalytical chemistry》2003,376(8):1149-1150
118.
J?rg Libuda 《Chemphyschem》2004,5(5):625-631
Reaction kinetics on nanometer-scale particles are different from those on extended surfaces of bulk materials. This fact has been utilized for a long time to empirically maximize the performance of heterogeneous catalysts, but the understanding of the underlying effects is poor at the microscopic level. Modern molecular beam-based methods, however, allow us to derive very detailed kinetic information on catalytically active surfaces. In combination with structurally highly controlled model catalysts, microscopic insights into the activity and selectivity of specific reaction centers on catalyst nanoparticles can be obtained. This combined approach is illustrated through simple model reactions. 相似文献
119.
A method is presented for the determination of dihydrostreptomycin in milk, muscle and kidney by reversed-phase ion-pair high-performance liquid chromatography and post-column derivatisation with beta-naphthoquinone-4-sulfonate prior to fluorescence detection. The new sample work-up procedures include acid precipitation of proteins and, in the case of muscle and kidney, removal of fats by solvent extraction followed by solid phase extraction on a cation exchanger. The fluorescence response was linear from 25 to 2000 micrograms l-1 of injected analyte. The detection limits were 10 micrograms kg-1 for milk and 15 micrograms kg-1 for muscle and kidney and the analyte recoveries were on average 93% for milk, 70% for kidney and 75% for muscle. 相似文献
120.
Mycotoxins are secondary metabolites, formed by the action of fungi on agricultural crops in the field or during storage. These metabolites are highly toxic to animals and humans and high levels have been measured in agricultural crops. In order to evaluate human risks due to ingestion of mycotoxin-contaminated food different methods have been developed for analysis of mycotoxins in cereals and maize. In this project the focus was on mycotoxins in agricultural soil and the fate of these toxins in the soil-water-plant system. Two different mycotoxins were selected in the study: zearalenone (ZON) produced by species of Fusariumor Aspergillusand ochratoxin A (OTA) produced by species of Penicillium. We developed a method for analysis of these toxins in soil. Soil samples were extracted with methanol-water (9:1) and purified by solid-phase extraction (SPE, C8-columns). The final extract was analysed using high-pressure liquid chromatography (HPLC) with fluorescence detection. A Phenyl Hexyl column was used to separate the toxins. The detection limits obtained were 0.1 and 1.0 microg kg(-1) dry weight (dw) for OTA and ZON, respectively. The developed method has been used for analysis of different soils in connection with growth chamber experiments. The soil types used in the growth chamber experiments were a sandy soil, a sandy clay soil, and a soil with high content of organic matter. The recovery was determined as 85.8 and 93.4% and the repeatability to 5.1 and 12.8% for OTA and ZON, respectively. The reproducibility obtained was 8.5 and 15.0% for soil samples, representing concentration levels from 0.2-30 microg kg(-1) dw (OTA) and from 1.0-100 microg kg(-1) dw (ZON). 相似文献