全文获取类型
收费全文 | 2268篇 |
免费 | 165篇 |
国内免费 | 216篇 |
专业分类
化学 | 1698篇 |
晶体学 | 48篇 |
力学 | 36篇 |
综合类 | 17篇 |
数学 | 62篇 |
物理学 | 788篇 |
出版年
2024年 | 4篇 |
2023年 | 28篇 |
2022年 | 44篇 |
2021年 | 60篇 |
2020年 | 55篇 |
2019年 | 78篇 |
2018年 | 41篇 |
2017年 | 83篇 |
2016年 | 81篇 |
2015年 | 84篇 |
2014年 | 106篇 |
2013年 | 218篇 |
2012年 | 110篇 |
2011年 | 141篇 |
2010年 | 140篇 |
2009年 | 138篇 |
2008年 | 108篇 |
2007年 | 148篇 |
2006年 | 133篇 |
2005年 | 132篇 |
2004年 | 115篇 |
2003年 | 78篇 |
2002年 | 73篇 |
2001年 | 74篇 |
2000年 | 58篇 |
1999年 | 44篇 |
1998年 | 54篇 |
1997年 | 38篇 |
1996年 | 31篇 |
1995年 | 23篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 15篇 |
1991年 | 16篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 9篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有2649条查询结果,搜索用时 0 毫秒
91.
Lijun Zhang Xun Hu Chengzhong Yu Russell Crawford 《International journal of environmental analytical chemistry》2013,93(12):1274-1285
A new solid phase extractant, sinapinaldehyde (SA) modified SBA-15 mesoporous silica, was developed for selective extraction and preconcentration of trace Pb(II) from aqueous solutions. The successful immobilization of SA on SBA-15 and the strong interaction between SA-SBA-15 and Pb(II) were characterized and confirmed by FTIR spectroscopy and scanning electron microscopy. Parameters such as solution pH, shaking time, eluent condition and sample volume were optimized so that the maximum removal of Pb(II) from solution could be achieved. At pH 4.0, the maximum adsorption capacity of the sorbent for Pb(II) was found to be 33.6?mg?g?1 and the adsorbed Pb(II) could be completely eluted using a mixed solution of 2?M HCl and 5% CS(NH2)2. Some common metal ions such as K(I), Na(I), Mg(II), Ca(II), Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) did not interfere with the adsorption of trace Pb(II). The detection limit of the present method was found to be 1.3?ng?mL?1 and the relative standard deviation was less than 2.0% (n?=?8). These results suggested that this new sorbent is very efficient and selective for the removal of trace Pb(II) in water samples. 相似文献
92.
K. Wallmann M. Kersten J. Gruber U. Förstner 《International journal of environmental analytical chemistry》2013,93(1-4):187-200
Abstract The binding forms of Co, Cd, Cu, Pb, and Zn in an anoxic, sulfide-bearing sediment were investigated by performing both thermodynamic equilibrium calculations and sequential extractions. Care was taken to maintain oxygen-free conditions during the whole experiment. The calculations suggested that trace metals were bound to sulfidic minerals. Sequential extraction results, however, showed increased importance of exchangeable and reducible fractions in the order Cu < Cd < Pb < Zn < Co. Thermodynamic equilibrium calculations of the chemical reactions during extraction showed that Cd, Co, Pb, and Zn sulfides are to a significant extent soluble in the acetate-exchangeable (step 1 + 2) and oxalate-reducible (step 3) fractions. Neglecting the dissolution of sulfide minerals would lead to a misinterpretation of the experimental results. 相似文献
93.
M. F. Hussain M. Katyal B. K. Puri Y. Takagi 《International journal of environmental analytical chemistry》2013,93(4):525-531
Abstract A sensitive method has been developed for the direct atomic absorption spectrometric determination of zinc, antimony and lead after coprecipitation of their trifluoroethylxanthates onto microcrystalline naphthalene. The metal xanthates are quantitatively coprecipitated over the pH ranges: Zn, 5.9–8.4; Sb, 4.0–6.0 and Pb, 4.0–11.0. The solid mass consisting of the metal complex and naphthalene is dissolved in DMF. This solution is aspirated into an air-acetylene flame at 213.9, 217.6 and 217.0nm for Zn, Sb and Pb, respectively. Beer's law is obeyed in the concentration range 2–50, 3–90 and 5–60 μg of Zn, Sb and Pb, respectively in 10ml of the final DMF solution. RSDs are at the ± (0.5–0.6)% level (n=10). The concentration for 1% absorption is 0.019, 0.035 and 0.060μg/ml for Zn, Sb and Pb, respectively. The method is suitable for the preconcentration of the metals from a larger volume of the aqueous phase, and has been employed for their determination in standard reference materials. It may be employed for the simultaneous determination of Zn, Pb and Sb in a solution by pH control. 相似文献
94.
95.
ABSTRACTThe reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH2) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10?13?cm3?molecule?1?s?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10?13?cm3?molecule?1?s?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH2 is 1.71?×?10?15?cm3?molecule?1?s?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH3. 相似文献
96.
A. R. Crosland S. P. McGrath P. W. Lane 《International journal of environmental analytical chemistry》2013,93(1-4):153-160
Abstract A standardised EDTA extraction procedure was tested collaboratively by six laboratories using two in-house reference soils identified as soil A and soil B. The extracts were analysed for Zn, Cu, Pb and Mn by Inductively Coupled Plasma Spectrometry. Concentrations of extractable elements in soil A were generally much lower than those found in soil B. All laboratories produced some extreme outlying results, most of these were produced in soil B. Results for Mn were the most variable, with a range of 63.4–100.3 μg g?1 in soil A and 226.4–415.3 μg g?1 in soil B. In both soils, one laboratory reported high values for Zn and Mn and, one laboratory, for soil B, produced values for all four elements which were consistently low. If outlying results are ignored, the results from most laboratories were in reasonable agreement for all elements except Mn. 相似文献
97.
John Liggio Robert Mclaren 《International journal of environmental analytical chemistry》2013,93(10):819-835
A method has been developed to measure aldehydes and ketones associated with atmospheric particles. Carbonyl compounds from particulate material collected on Teflon-coated glass-fiber filters were simultaneously extracted and derivatized with an appropriate 2,4-dinitrophenylhydrazine (2,4-DNPH) solution. The efficiency of this procedure utilizing various 2,4-DNPH concentrations and solvent compositions was studied for 13 carbonyl compounds of atmospheric importance. These include formaldehyde, acetaldehyde, acetone, dicarbonyls such as glyoxal and methylglyoxal, and biogenic carbonyls such as pinonaldehyde and nopinone. An extraction solution containing 3 × 10?2 M 2,4-DNPH, in 60% acetonitrile/40% water, and pH 3 was most efficient in extracting and derivatizing these aldehydes and ketones (83-100% recovery). Improved sample enrichment and 2,4-DNPH purification methods were developed that afforded detection limits of 0.009-5.6 ng m?3. The relative standard deviation for replicate analyses were 1.9-10.1%. Carbonyl compounds in ambient particulate samples were quantified during a recent field study. Median values for nine carbonyl species ranged from 0.01-33.9 ng m?3 during the study. 相似文献
98.
A. Haunold E. Rosenberg M. Grasserbauer 《International journal of environmental analytical chemistry》2013,93(1-4):157-172
Abstract Reliable and comprehensive sampling methods are required to obtain accurate data for VOC concentrations in air samples. The major drawback of the adsorption tube sampling method, widely employed in environmental studies, is the fact that C2 compounds are usually not trapped quantitatively. The focus of this work was thus to improve sampling based on adsorption tubes packed with Molsieve and Carbosieve. To improve the sampling efficiency for the C2 compounds, a cooling device, based on Peltier cooling was constructed, which could be operated at a temperature down to ?30°C. Experiments under laboratory and field conditions were carried out to study the influence of the sampling temperatuie on the recovery of ethane and ethene as the most volatile VOCs. The results clearly demonstrate the need for a cooled sampling device for the analysis of C2 compounds in air. Under the investigated conditions, the recoveries with ambient temperature sampling were only in the range of 38–46% for ethane and 33–59% for ethene respectively, in comparison to the cooled sampling device. These findings are only valid for the described conditions and can change significantly with temperature and concentration. A generalisation of the recovery is thus very difficult to give. The use of the sampling device for a field study is reported, where samples were collected simultaneously at three different altitudes in a diurnal profile on the slope of the Schulterberg mountain in Tyrol (Austria). 相似文献
99.
Hydride generation atomic fluorescence spectrometry (HG-AFS) is used for the determination of hydride-forming elements due to its high sensitivity, simplicity, and low cost. A new HG-AFS method for the simultaneous determination of arsenic and lead in vegetable oil is reported. Vortex-assisted extraction with dilute nitric acid was used to isolate arsenic and lead from vegetable oil. The conditions influencing the fluorescence signal, including the carrier fluid, oxidizing agent, and reducing agent, were optimized. The interferences of coexisting ions were also evaluated. Under the optimized conditions, the limits of detection were 0.6 and 0.4?µg?kg?1 for arsenic and lead. The recoveries were from 84.4 to 105% for both metals in vegetable oil. The optimized method was used for the determination of arsenic and lead in commercial vegetable oil. The analytical results by this approach were in good agreement with values obtained by inductively coupled plasma mass spectrometry with microwave digestion. 相似文献
100.
A nitrate ion selective electrode (nitrate-ISE) based on pyrrole modification on a common pencil lead was proposed. The lab-made nitrate-ISE was easily constructed by pyrrole polymerization with nitrate ion as the dopant using cyclic voltammetry. The fabricated nitrate-ISE was then coupled with flow injection analysis (FIA) for an automatic system. The flow potentiometry provided working range of 1x10-4 to 4x10-3 mol L-1 of nitrate and allowed sample throughput up to 50 samples h-1. Linear regression analysis showed good agreement (r2=0.9961) with Nernstian response. This system was applied to determine nitrate-nitrogen (nitrate-N) in fertilizer samples. 相似文献