全文获取类型
收费全文 | 1968篇 |
免费 | 66篇 |
国内免费 | 16篇 |
专业分类
化学 | 1472篇 |
晶体学 | 16篇 |
力学 | 71篇 |
数学 | 175篇 |
物理学 | 316篇 |
出版年
2024年 | 4篇 |
2023年 | 12篇 |
2022年 | 54篇 |
2021年 | 97篇 |
2020年 | 65篇 |
2019年 | 66篇 |
2018年 | 54篇 |
2017年 | 54篇 |
2016年 | 72篇 |
2015年 | 56篇 |
2014年 | 77篇 |
2013年 | 166篇 |
2012年 | 121篇 |
2011年 | 121篇 |
2010年 | 80篇 |
2009年 | 79篇 |
2008年 | 93篇 |
2007年 | 117篇 |
2006年 | 77篇 |
2005年 | 80篇 |
2004年 | 79篇 |
2003年 | 55篇 |
2002年 | 54篇 |
2001年 | 18篇 |
2000年 | 21篇 |
1999年 | 18篇 |
1998年 | 8篇 |
1997年 | 15篇 |
1996年 | 18篇 |
1995年 | 8篇 |
1994年 | 9篇 |
1993年 | 11篇 |
1992年 | 15篇 |
1991年 | 16篇 |
1990年 | 9篇 |
1989年 | 15篇 |
1988年 | 8篇 |
1987年 | 11篇 |
1986年 | 7篇 |
1985年 | 19篇 |
1984年 | 5篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 9篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1973年 | 4篇 |
排序方式: 共有2050条查询结果,搜索用时 31 毫秒
41.
Katritzky AR Akhmedov NG Abdel-Fattah AA Wang M Rostek CJ Maender OW 《Magnetic resonance in chemistry : MRC》2004,42(5):424-435
Nucleophilic addition of alkyl- and benzylthiols to benzoquinone diimine (1) gave the corresponding 3-alkylthio- or 3-benzylthio-1,4-phenylenediamines (2-5). However, addition of aryl- or heteroarylthiols to 1 formed 2-arylthio- or 2-heteroarylthio-1,4-phenylenediamines (6-14). The structures of 2-14, obtained in 55-91% yields, were confirmed in CDCl3 or DMSO-d6 solution using 1D (NOE difference, coupled 13C NMR spectra, APT and DEPT) and 2D NMR techniques [DQCOSY, NOESY, HETCOR and heteronuclear multiple bond coherence (HMBC)] that resulted in unambiguous proton and carbon NMR resonance assignments. The substituent-induced 13C NMR chemical shift differences were calculated in 2-14 relative to carbon atoms in the model compound N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamine (DMBPPD) (15) (a reduced form of benzoquinone diimine). 相似文献
42.
Khalil A. Abboud Peter N. Nickias Eugene Y.‐X. Chen 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):m41-m42
In the structure of bis({N‐[dimethyl(1η5‐2,3,4,6‐tetramethylindenyl)silyl]cyclohexylamido‐1κN}(methyl‐3κC)‐di‐μ3‐methylene‐1:2:3κ3C;1:3:3′κ3C‐tris(pentafluorophenyl‐2κC)titanium) benzene disolvate, [Me2Si(η5‐2,3,4,6‐Me4C9H2)(C6H11N)]Ti[(μ3‐CH2)Al(C6F5)3][AlMe(μ3‐CH2)]2 or [Ti2(C21H7AlF15)2(C21H31NSi)2]·2C6D6, the dimer is located on an inversion center, and the two Ti centers are linked by double Ti(μ3‐CH2)Al(C6F5)3AlMe(μ3‐CH2) heterocycles. The electron‐deficient Ti centers are further stabilized by two α‐agostic interactions between Ti and one H atom of each bridging methylene group. 相似文献
43.
Some new N‐glycosides of 4‐(2‐phenylethyl)‐5‐pyridyl‐1,2,4‐triazole‐3‐thiones were synthesised by the coupling reaction of halo sugar with 4,5‐disubstituted 3H‐1,2,4‐triazole‐3‐thiones in the presence of mercuric cyanide and dry nitromethane as solvent, followed by deprotection using dry ammonia in methanol. All of the above compounds were fully characterized by means of infrared, 1H NMR spectroscopy, mass spectroscopy and elemental analysis. 相似文献
44.
A novel membrane sensor for selective monitoring of iodide, consisting of a triiodide‐ketoconazole ion pair complex dispersed in a PVC matrix, plasticized with a mixture of 2‐nitrophenyl octyl ether and dioctylphtalate with unique selectivity toward iodide ions, is described. The influence of membrane composition, pH of test solution and foreign ions on the electrode performance were investigated. The optimized membrane demonstrates a near‐Nernstian response for iodide ions over a wide linear range from 1.0 × 10?2 to 1.0 × 10?5 M, at 25 ± 1 °C. The electrode could be used over a wide pH range 3–10 and has the advantages of high selectivity, fast response time and good lifetime (over 4 months). It was successfully used as indicator electrode in potentiometric titrations and direct potentiometric assay of iodide ions. 相似文献
45.
M. Ashraf Chaudry Noor-ul-Islam Niaz-ur-Rahman 《Journal of Radioanalytical and Nuclear Chemistry》1997,218(1):53-60
Membranes, based on tri-n-octylamine (TOA) xylene liquid, supported in hydrophobic microporous films have been used to study the transport of Pd(II) ions, after extraction into the membrane. Various parameters, such as the effect of hydrochloric acid concentration in the feed solution, TOA concentration in the membrane phase, effect of stripping agent like nitric acid concentration, and temperature on the flux of Pd(II) ions across the liquid membranes have been investigated. The optimum conditions of transport for these metal ions determined are, TOA concentration, 1.25 mol·dm–3, HCl concentration in the feed solution, 5 mol·dm–3, and concentration of nitric acid used as a stripping, agent 5 mol·dm–3. The maximum values of the flux and permeability determined under the optimum condition are 23·10–6 mol·m–2·s–1 and 2.40·103 m2·s–1 at 25°C. The results obtained have been used to elucidate the mechanism of palladium transport. 相似文献
46.
M. Ashraf Chaudry Noor-Ul-Islam Naeem-Ur-Rehman Zafar Yasin 《Journal of Radioanalytical and Nuclear Chemistry》1995,189(2):207-218
The role of nitrate ions in uranyl ions transport across TBP-kerosene oil supported liquid membranes (SLM) at varied concentrations of HNO3 and NaNO3 has been studied. It has been found that nitrate ions move faster compared to uranyl ions at the uranium feed solution concentrations studied. The nitrate to uranyl ions flux ratio vary from 355 to 2636 under different chemical conditions. At low uranium concentration the nitrate ions transport as HNO3 · TBP, in addition to as UO2(NO3)2 · 2TBP type complex species. The flux of nitrate ions is of the order of 12.10 · 10–3 mol · m–2 · s–1 compared to that of uranium ions (4.56 · 10–6 mol · m–2 · s–1). The permeability coefficient of the membrane for nitrate ions varies with chemical composition of the feed solution and is in the order of 2.5 · 10–10 m–2 · s–1. The data is useful to estimate the nitrate ions required to move a given amount of uranyl ions across such an SLM and in simple solvent extraction. 相似文献
47.
An unprecedented one-pot reductive trimerization of aromatic aldehydes to 1,2,3-triaryl-2-propen-1-ones as well as tandem reductive coupling-rearrangements of aryl ketones to pinacolone analogues was efficiently achieved using tetrachlorosilane-zinc at room temperature. 相似文献
48.
Ali Taha Viktor Gutmann Wolfgang Linert 《Monatshefte für Chemie / Chemical Monthly》1991,122(5):327-339
Summary The solvatochromic and thermochromic behaviour of a series of mixed Ni(II) complexes with unsubstituted and substituted -diketones and diamines in the solvents 1,2-dichloroethane (DCE), acetonitrile (An), acetone (AC),n-butanol (n-BuOH), formamide (FA), N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and pyridine (PY) has been studied and characterized on the basis of electronic spectra. Spectrophotometric methods have been used to evaluate equilibrium constants and their enthalpic and entropic terms for the formation of Ni(-dik)(diam)L
+ and Ni(-dik)(diam)L
2
+
. Increasing donor strength of the donor-solvents (L) and (or) increasing electronwithdrawing parameters of the substituents at the -diketone and the diamine ligands lead to increasing formation constants, paralleled by relative increase in the stability of the five-coordinated species Ni(-dik)(diam)L
+. The results are discussed in terms of the extended donor-acceptor concept.On leave of absence from the Faculty of Education, Ain Schams University, Roxy, Cairo, Egypt 相似文献
49.
50.
Sorption of uranium by non-living water hyacinth roots 总被引:1,自引:0,他引:1
S. Shawky M. Abdel Geleel Ashraf Aly 《Journal of Radioanalytical and Nuclear Chemistry》2005,265(1):81-84
Summary Many studies have shown that water hyacinth (Eichhornia crassipes) roots can be used to accumulate high concentrations of organic as well as inorganic pollutants. They are currently used to remediate aquatic environments and aqueous solutions. In the present study, sorption of uranium from aqueous solutions by using dried roots of water hyacinth has been investigated. The sorption of uranium was examined as a function of initial concentration, pH, weight of roots and contact time. Five different concentrations 20, 40, 60, 80, and 100 μg . ml-1 were used. Sorption proves to be very rapid and depend on pH, weight of roots and concentration of uranium. Maximum sorption capacity of water hyacinth roots was 64,000 U6+ μg/g. The sorption of uranium by water hyacinth roots follows a Langmuir isotherm. 相似文献