全文获取类型
收费全文 | 1664篇 |
免费 | 55篇 |
国内免费 | 8篇 |
专业分类
化学 | 1017篇 |
晶体学 | 20篇 |
力学 | 61篇 |
数学 | 223篇 |
物理学 | 406篇 |
出版年
2023年 | 10篇 |
2022年 | 50篇 |
2021年 | 61篇 |
2020年 | 35篇 |
2019年 | 42篇 |
2018年 | 52篇 |
2017年 | 33篇 |
2016年 | 52篇 |
2015年 | 59篇 |
2014年 | 61篇 |
2013年 | 130篇 |
2012年 | 126篇 |
2011年 | 123篇 |
2010年 | 79篇 |
2009年 | 87篇 |
2008年 | 99篇 |
2007年 | 91篇 |
2006年 | 63篇 |
2005年 | 60篇 |
2004年 | 55篇 |
2003年 | 41篇 |
2002年 | 38篇 |
2001年 | 33篇 |
2000年 | 30篇 |
1999年 | 28篇 |
1998年 | 12篇 |
1997年 | 15篇 |
1996年 | 18篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 18篇 |
1992年 | 17篇 |
1991年 | 14篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有1727条查询结果,搜索用时 15 毫秒
21.
Determination of trace elements in biological materials using tetramethylammonium hydroxide for sample preparation 总被引:1,自引:0,他引:1
Patrícia Martins Dirce Pozebon Valderi L. Dressler Gisele A. Kemieciki 《Analytica chimica acta》2002,470(2):62-204
A method to prepare milk powder, bovine liver and bovine muscle samples for analysis by electrothermal atomic absorption spectrometry (ETAAS) is proposed. Samples are mixed with a small amount of tetramethylammonium hydroxide (TMAH) and a stable and homogeneous slurry is produced in ca. 2 h with heating at 60–70 °C. After such sample preparation and dilution with water, trace elements are determined in certified reference materials. Pyrolysis and atomisation temperatures are optimised for each element, and several modifiers are investigated. External calibration is used for every analyte. Limits of detection (LODs), precision and accuracy are reported for Cd, Pb, Ni, Cr, Cu and Ag and compared with those obtained after conventional acid digestion. The main advantages of the proposed method are the simplicity of sample preparation and the longer lifetime of the graphite tube. 相似文献
22.
rico Marlon de Moraes Flores Ana Paula Fleig Saidelles Eder Lisandro de Moraes Flores Mrcia Foster Mesko Mrcio Pozzobon Pedroso Valderi Luiz Dressler Celso Figueiredo Bittencourt Adilson Ben da Costa 《Microchemical Journal》2004,77(2):113-118
An alternative device for the direct solid analysis (DSA) for copper determination by flame atomic absorption spectrometry (FAAS) is proposed. Copper was directly determined in commercial medicinal plants used as dietary supplements. The determination of copper in solid samples by DSA–FAAS was made by using a conventional air–acetylene flame. Between 0.05 and 1.5 mg of each test, sample was weighed directly into a small polyethylene vial connected to the device used for solid introduction into the flame. Test samples were introduced into the flame as a dry aerosol using a T-quartz cell set between the burner and the optical path. The T-quartz cell has a slit in the superior part by which the solid aerosol passes to the flame. A transient signal, evaluated as integrated absorbance, is produced and it is totally integrated in 2 s. Background signals always presented absorbance values less than 0.1. It was found a characteristic mass of 0.8 ng Cu and absolute limit of detection of 1.2 ng (3 s), or 1.2 μg g−1 if a sample mass of 1 mg was used. Optimized conditions for air flow rate, flame stoichiometry, and so on were established as well. No excessive grinding of the samples was needed and samples with particle of size less than 80 μm were used throughout. No statistical difference between the results from the proposed system and those obtained by sample digestion and determination by conventional FAAS was observed. With the proposed procedure, more than 50 test samples can be analyzed in 1 h and it can be easily adapted to conventional spectrometers for FAAS. 相似文献
23.
24.
25.
E. Bütkus J. C. Martins U. Berg 《Journal of inclusion phenomena and macrocyclic chemistry》1996,25(1-3):125-128
- and -cyclodextrins were found to form 1:1 inclusion complexes with 2,6- and 2,9-substituted bicyclo[3.3.1]nonanes. The binding constants and the structure of the complexes were estimated from titration studies and 2D ROESY experiments. 相似文献
26.
27.
The present work describes a metallic hydride atomizer for atomic absorption spectrometry, by evaluating the performance of the Inconel 600® tube. For this purpose, stibine was used as the model volatile compound and antimony determination in river and lake sediments and in pharmaceutical samples was carried out to assess the metal furnace performance. Some parameters are evaluated such as those referring to the generation and transport of the hydride (such as KBH4 and acid concentrations, carrier gas flow rate, injected volume, etc.), as well as those referring to the metal furnace (such as tube hole area, flame composition, long-term stability, etc.). The method presents linear Sb concentration from 2 to 80 μg L−1 range (r > 0.998; n = 3) and the analytical frequency of ca. 140 h−1. The limit of detection (LOD) is 0.23 μg L−1 and the precision, expressed as R.S.D., is less than 5% (40 μg L−1; n = 10). The accuracy is evaluated through the reference materials, and the results are similar at 95% confidence level according to the t-test. 相似文献
28.
Filho HP 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(11):2627-2633
The polar tensors of cis and trans-1,2-difluoroethylenes have been determined with new normal modes based in a reassignment of nu(7) and nu(12) bands of the trans isomers and frequency values corrected for Fermi resonances and phase shifts. The signs of the dipole moment derivatives (and its directions, for B(u) symmetry species) were considered to be those of MP2/6-31G** estimates. Root mean square errors calculated for the new tensor element values from each pair of isotopomers (trans-1,2-C(2)H(2)F(2)/trans-1,2-C(2)D(2)F(2) and cis-1,2-C(2)H(2)F(2)/cis-1,2-C(2)D(2)F(2)) show that the new polar tensor sets fit the isotopic invariance criterion better than previously reported sets. The accuracy of polar tensor transference procedures was tested by calculating the infrared intensities of trans-1,2-C(2)H(2)F(2) through the new polar tensors of the cis isomer. The resulting estimates are very accurate and also support the new band assignment, though the A(6) intensity remains still somewhat underestimated. 相似文献
29.
Vincent BailliezRenata M. de Figueiredo Alain OleskerJeannine Cleophax 《Tetrahedron letters》2003,44(51):9151-9153
The macrocyclic core of cycloviracin and glucolipsin has been synthesised in ten steps from levoglucosan and (S)-(−)-dimethyl malate. The limited number of steps to obtain this macrolide makes it a valuable procedure for the synthesis of analogues of cycloviracin and glucolipsin. 相似文献
30.
The temperature calibration on cooling of thermal analysis instruments is important for the accurate study of the non-isothermal crystallization kinetics of semi-crystalline polymers. In previous works, a methodology was proposed for performing the calibration on cooling of differential scanning calorimeters (DSCs) with standard metals, and the calibration errors were checked using transitions of high-purity liquid crystals. In this work, alternative, physically meaningful, procedures for carrying out the calibration on cooling are analyzed and validated. The calibration errors are evaluated also with liquid crystalline transitions, when the calibration is performed with standard metals, in a wide temperature range, and when due account is taken for the need of isothermal corrections to the temperature measurements. It is shown that any pair of standard metals may be used to calibrate on cooling, that the calibration errors increase for wider working temperature ranges and that, providing that certain conditions are fulfilled, both calibration procedures yield similar results. 相似文献