首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   5442篇
  免费   531篇
  国内免费   665篇
化学   3824篇
晶体学   48篇
力学   962篇
综合类   12篇
数学   448篇
物理学   1344篇
  2024年   10篇
  2023年   118篇
  2022年   92篇
  2021年   88篇
  2020年   105篇
  2019年   86篇
  2018年   105篇
  2017年   150篇
  2016年   233篇
  2015年   254篇
  2014年   266篇
  2013年   380篇
  2012年   345篇
  2011年   429篇
  2010年   322篇
  2009年   336篇
  2008年   312篇
  2007年   350篇
  2006年   322篇
  2005年   306篇
  2004年   311篇
  2003年   229篇
  2002年   206篇
  2001年   160篇
  2000年   168篇
  1999年   156篇
  1998年   114篇
  1997年   118篇
  1996年   111篇
  1995年   106篇
  1994年   58篇
  1993年   50篇
  1992年   42篇
  1991年   45篇
  1990年   33篇
  1989年   26篇
  1988年   17篇
  1987年   16篇
  1986年   8篇
  1985年   8篇
  1984年   11篇
  1983年   3篇
  1982年   4篇
  1981年   9篇
  1977年   2篇
  1976年   4篇
  1974年   2篇
  1973年   2篇
  1971年   3篇
  1957年   3篇
排序方式: 共有6638条查询结果,搜索用时 31 毫秒
991.
This paper studies contact processes on general countable groups. It is shown that any such contact process has a well-defined exponential growth rate, and this quantity is used to study the process. In particular, it is proved that on any nonamenable group, the critical contact process dies out. Research supported by GAČR grant 201/06/1323 and the German Science Foundation. Part of this work was carried out when the author was employed as a postdoc at the University of Tübingen.  相似文献   
992.
Microwave assisted micellar extraction (MAME) coupled with solid phase microextraction (SPME) and HPLC-UV determination have been used for the determination of five organochlorine pesticides from agricultural soil samples. A non-ionic surfactant, Polyoxyethlylene 10 Lauryl Ether was used, and the different variables for the optimization of MAME and SPME procedures were studied. This method was applied successfully to the determination of these pesticides in several kinds of agricultural soil samples with different characteristics. Most of the compounds studied can be recovered in good yields with R.S.D. lower than 9% and detection limit ranged between 56-96 ng g−1 for the pesticides studied.  相似文献   
993.
Fan SL  Zhang LK  Lin JM 《Talanta》2006,68(3):646-652
Based on the sensitizing effect of formic acid on the chemiluminescence (CL) reaction of polyhydroxylbenzenes with acidified potassium permanganate and the combination technique of high-performance liquid chromatography (HPLC), a sensitive, selective and simple post-column CL detection method for simultaneously determining catechol, resorcinol, hydroquinone and 1,2,4-benzenetriol is described. The optimal conditions for the CL detection and HPLC separation were carried out. The linear ranges were: 6.0 × 10−3-1.5 mg/L for hydroquinone, 8.0 × 10−3-1.5 mg/L for 1,2,4-benzenetriol, 1.0 × 10−2-2.0 mg/L for resorcinol and 1.0 × 10−2-2.5 mg/L for catechol, respectively. The detection limits are: 3.2 × 10−3 mg/L for hydroquinone, 3.9 × 10−3 mg/L for 1,2,4-benzenetriol, 4.7 × 10−3 mg/L for resorcinol and 5.2 × 10−3 mg/L for catechol, respectively. Combining with solid phase extraction, the proposed method has been successfully applied to the determination of the polyhydroxylbenzenes in river water. The recoveries for three benzentriols were 92.1-95.4% and 82.0% for 1,2,4-benzenetriol, respectively.  相似文献   
994.
Although the use of once widely applied selective herbicide, 4,6-dinitro-o-cresol (DNOC), was cancelled by US-EPA in 1987, it is still found in soil and water due to its slow degradation in the environment. Since solid phase extraction-spectrophotometry combinations are much simpler and cheaper than chromatography/MS based methods and most routine laboratories lack such sophisticated instrumentation, it is desirable to establish novel sensitive, well-established, and field-applicable spectrophotometric methods for the rapid assay of DNOC in water and soil. For this purpose, two distinct spectrophotometric methods utilizing the periodate and copper(II)-neocuproine (Nc) reagents have been developed following Zn/HCl reduction of the pesticide in a microwave oven for 15 s, and validated for DNOC determination at mg L−1 level. The LOD values were 1.6 and 0.2 mg L−1 for periodate and Cu(II)-Nc methods, respectively. Statistical comparison of the developed methods was made with the aid of high performance liquid chromatography (HPLC) equipped with a C18 (5 μm), 250 mm× 4.6 mm ID reversed phase column in conjunction with a UV (264 nm) detector, and a methanol (HPLC grade) +0.1% glacial acetic acid mixture mobile phase. Both spectrophotometric methods were directly applicable to soil since they were not interfered with common soil cations and anions, together with some pesticides. These methods were applied to real samples such as synthetically contaminated montmorillonite and lemon juice, and overall recovery efficiencies at the order of 95% or greater were achieved in the devised adsorption/elution procedures. An 8-hydroxyquinoline (oxine)-impregnated XAD copolymer resin stabilized with Fe(III) salt was used to preconcentrate DNOC at a concentration factor of 20 from lemon juice contaminated with 1 mg L−1 DNOC, and the analyte retained at pH 2.5 was eluted with 0.025 M methanolic NaOH. Both the devised spectrophotometric methods and the proposed preconcentration column with optimized sorption and desorption conditions are novel for DNOC assay in the natural environment.  相似文献   
995.
Grobecker KH  Detcheva A 《Talanta》2006,70(5):962-965
Certified reference materials (CRMs) of different origin were used to validate the direct determination of total mercury by solid sampling Zeeman atomic absorption spectrometry (SS-ZAAS) and a specially designed furnace. The temperature program provides only for one step. Atomisation of mercury and pyrolysis of the matrix is performed at a constant temperature in the range of 900–1000 °C. Calibration points achieved by CRMs and aqueous solutions are covered by one calibration line, indicating the absence of matrix effects. Relatively high amounts of chlorine, known for causing problems in mercury determination do not influence analytical results. The excellent accuracy of the method results in a very good agreement with the certified values. The precision of SS-ZAAS measurements in a range from 0.5 to 50 ng Hg does not exceed 3% R.S.D. A limit of quantification of 0.008 μg g−1 Hg was achieved.  相似文献   
996.
Malik AK  Kaur V  Verma N 《Talanta》2006,68(3):842-849
This paper reviews the practical applications of solid phase microextraction-High performance liquid chromatography in the analysis of toxic metal species as these are important contaminants and are carcinogenic. Their determination in formulations, in feed and food, and in complex environmental matrices (e.g., waste water and industrial effluents) often requires analytical methods capable of high efficiency, unique selectivity, and high sensitivity. Solid phase microextraction (SPME) requires low solvent consumption and is quick in use. SPME is used for extraction and online desorption of analytes with the mobile phase of HPLC and subsequent detection by UV, ICP-MS or ESI-MS as detectors. Different SPME-HPLC methods are summarized in this article to demonstrate the usefulness of this technique for metallic species of As, Cr, Pb, Hg and Se.  相似文献   
997.
Ali I  Gupta VK  Singh P  Pant HV 《Talanta》2006,68(3):928-931
Domperidone is a dopamine D2 receptor antogonist, which has been used as antiemetic agent in human beings. It has been found in wastewater released by some pharmaceutical industries leading to the contamination of surface and ground water. Therefore, a sensitive, inexpensive and reproducible HPLC-SPE method was developed for the analysis of domperidone in the wastewater. The column used was Waters symmetry C18 (15 cm × 0.46 mm, 5 μm). The mobile phase used was phosphate buffer (50 mM, pH 3.5) acetonitrile (80:20, v/v) at the flow rate 2.0 mL/min. The detection was achieved by using UV mode at 230 nm. The retention, separation and resolution factors were 2.63, 3.00 and 3.20, respectively. The percentage recovery of domperidone from wastewater was 95.0%. Celiprolol was used as the internal standard to access the percentage extraction of domperidone from wastewater.  相似文献   
998.
Guo L  Dong W  Tong X  Dong C  Shuang S 《Talanta》2006,70(3):630-636
The fluorescence and solid substrate room temperature phosphorescence (SS-RTP) properties of Pd(II) meso-tetrakis (4-N-methyl-pyridiniumyl) porphyrin (Pd(II)TMPyP) were studied. The factors influencing the SS-RTP emission, such as filter type, inorganic salt sort, drying temperature, pre-drying time and drying time were investigated in detail. Strong SS-RTP signal can be induced on the slow speed filter paper in the presence of the external inorganic salt, Ca(NO3)2, with the maximum excitation and emission wavelengths at 421 nm and 675 nm, respectively. The interaction between calf thymus DNA (ctDNA) and Pd(II)TMPyP was investigated at pH 7.2 using SS-RTP, fluorescence and UV-vis spectroscopy. The SS-RTP intensity of Pd(II)TMPyP was enhanced efficiently with the increasing amount of ctDNA. This phenomenon demonstrates that the intercalated porphyrin is shielded by ctDNA to avoid collision quenching. This result was supported by SS-RTP lifetime measurement, SS-RTP anion quenching experiment and fluorescence polarization measurement. Furthermore, with the addition of ctDNA, the UV-vis spectra of Pd(II)TMPyP shows apparent hypochromicity (40%) at the Soret maximum of 417 nm and a red shift of Δλ = 15 nm, also indicating that Pd(II)TMPyP intercalates into ctDNA bases. The binding constant of Pd(II)TMPyP to ctDNA was calculated to be 4.41 × 105 L/mol based on the derivative McGhee-von Hippel plots.  相似文献   
999.
Tsc-protected ε-amino acids, bicyclo[3.3.0]octane-5-amino-1-carboxylic acids (1), ready to use in the solid-phase synthesis, are prepared from 4,4-diethylcarboxylic bicyclo[3.3.0]oct-2-enone (3), which is available in bulk from 2 through the catalytic Pauson-Khand reaction.  相似文献   
1000.
The lattice parameter changes with respect to temperature (T) have been measured by high temperature X-ray diffraction (HTXRD) technique for ThO2NdO1.5 solid solutions containing 23.8 and 42.5 mol% NdO1.5 in the temperature range from 298 to 2000 K. The temperature versus lattice parameter data have been made use of in calculating the lattice thermal expansivity. The values of thermal expansion of the solid solutions were found to be increased with increase in neodymium oxide content and temperature. The mean linear thermal expansion coefficients in this temperature range for ThO2NdO1.5 solid solutions are 12.28 × 10−6 and 12.90 × 10−6 K−1, respectively. The binding energies of Th 4f7/2 and Nd 3d5/2 energy levels of the solid solutions containing 13.1, 23.8, 31.9, 37.2 and 42.5 mol% NdO1.5 and two-phase mixtures containing 47.6 and 51.8 mol% NdO1.5 were experimentally determined by X-ray photoelectron spectroscopy (XPS).  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号