全文获取类型
收费全文 | 1907篇 |
免费 | 75篇 |
国内免费 | 206篇 |
专业分类
化学 | 1579篇 |
晶体学 | 9篇 |
力学 | 125篇 |
综合类 | 1篇 |
数学 | 100篇 |
物理学 | 374篇 |
出版年
2024年 | 4篇 |
2023年 | 35篇 |
2022年 | 31篇 |
2021年 | 29篇 |
2020年 | 26篇 |
2019年 | 25篇 |
2018年 | 28篇 |
2017年 | 48篇 |
2016年 | 54篇 |
2015年 | 49篇 |
2014年 | 90篇 |
2013年 | 121篇 |
2012年 | 90篇 |
2011年 | 120篇 |
2010年 | 105篇 |
2009年 | 145篇 |
2008年 | 123篇 |
2007年 | 161篇 |
2006年 | 129篇 |
2005年 | 107篇 |
2004年 | 100篇 |
2003年 | 56篇 |
2002年 | 38篇 |
2001年 | 44篇 |
2000年 | 39篇 |
1999年 | 26篇 |
1998年 | 31篇 |
1997年 | 25篇 |
1996年 | 20篇 |
1995年 | 35篇 |
1994年 | 31篇 |
1993年 | 25篇 |
1992年 | 24篇 |
1991年 | 18篇 |
1990年 | 14篇 |
1989年 | 19篇 |
1988年 | 22篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 21篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 5篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 3篇 |
排序方式: 共有2188条查询结果,搜索用时 454 毫秒
71.
Ramapanicker Ramesh 《Tetrahedron》2007,63(37):9153-9162
The base catalyzed cyclization of N-aryl and N-alkyl-O-propargyl carbamates is studied in detail. The effect of various bases and solvents on the efficacy of this cyclization reaction is analyzed and a new base-solvent system (LiOH in DMF) for effective cyclization of these carbamates is reported. A number of differentially substituted O-propargyl carbamates were cyclized to the corresponding 2-oxazolidinones under these conditions. The reaction conditions reported here are mild and no side reactions were observed in any of the substrates studied. A propargyl carbonate group was unaffected during the course of the cyclization of the O-propargyl carbamate group. The propargyl carbamates were prepared from the corresponding alkyl or aryl amines and the corresponding propargyl chloroformate, resulting in oxazolidinones diversely substituted at the nitrogen atom. N-Aryl-O-propargyl carbamates cyclized readily to the corresponding oxazolidinones with LiOH in DMF, whereas N-alkyl-O-propargyl carbamates reacted slowly under the same conditions. O-Propargyl carbamates substituted at the 1-position tend to cyclize faster whereas those substituted at 3-position cyclize considerably slower than the unsubstituted carbamates. 相似文献
72.
Summary In this study a new approach is presented for on-line radiometric detection in reversed phase LC of medium to low polarity
compounds labelled with14C.
The test compounds,14C-carbaryl and14C-parathion, are extracted post-column into a non-water miscible liquid scintillation cocktail. The segmented two-phase system
formed is introduced into the beta-detector without phase separation and collected in a capillary storage tube.
After completion of the LC separation and detection process, the direction of the flow in the storage system is reversed and
the segmented contents of the loop led at lower flow-rates through the beta-detector again. An enhanced signal, corresponding
to the increase in counting time is obtained without measurable peak broadening.
The lowest possible detection limit of the system is 9 counts per peak corresponding to subnanogram quantities of tested pesticides.
Calibration curves are linear over at least 2 orders of magnitude and have the expected theoretical slopes.
The reproducibility of the system is better than 4 % rel. S.D. An application to a recovery study of parathion shows the practical
potential of this technique.
Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984 相似文献
73.
Lämmerhofer M 《Journal of chromatography. A》2005,1068(1):3-30
Enantiomer separations by CE employing nonaqueous conditions are reviewed. The general focus of this article is directed towards solvent effects on chiral recognition and the separation mechanism. After a general discussion of solvent effects on the individual processes involved in CE enantiomer separation, specifics for various selector classes are discussed together with a few applications of enantioselective nonaqueous CE. 相似文献
74.
Solvent effects in a carbenoid N-H insertion route to triarylamines via 2-diazo-1,3-cyclohexanedione
Peter Livant 《Tetrahedron letters》2005,46(12):2113-2116
The Rh-carbenoid derived from 2-diazo-1,3-cyclohexanedione inserts into the N-H bond of arylalkylamines and diarylamines. A solvent for this reactive carbenoid is suggested. The insertion products undergo a Pd-mediated aromatization to afford alkyldiarylamines and triarylamines. 相似文献
75.
76.
Poly(ethylene glycol) (PEG 3400) was used as a soluble polymeric support for the synthesis of a series of novel benzazepines. The key step for the preparation of these heterocycles was a phosphine-free palladium-catalyzed Heck reaction. Palladium nanoparticles formed during the course of the reaction were characterized. The presence of PEG 3400 influenced the outcome of the reaction in terms of selectivity. 相似文献
77.
78.
Toshio Fuchigami 《Journal of fluorine chemistry》2007,128(4):311-316
Recent studies on solvent effects on electrochemical partial fluorination are reviewed. At first, the historical background and some problems of electrochemical fluorination in organic solvents like acetonitrile (MeCN) are briefly mentioned. Ethereal solvents like dimethoxyethane (DME) and a mixture of DME and MeCN were found to improve both the yield and current efficiency for electrochemical fluorination since these solvent systems effectively suppress anode passivation and overoxidation of fluorinated products once formed during the electrolysis. It was also found that DME stabilizes radical cationic intermediates of 4-arylthio-1,3-dioxolan-2-ones and 3-phenylthiophthalide leading to α-fluorination while dichloromethane (CH2Cl2) destabilizes them leading to fluorodesulfurization. On the other hand, imidazolium ionic liquids and liquid fluoride salts like Et4NF·4HF and Et3N·5HF exhibited similar effects to CH2Cl2. Selective fluorination of hardly oxidizable phthalide was also achieved using a combination of two kinds of ionic liquids (imidazolium triflate and liquid fluoride salts). 相似文献
79.
不同类型聚合物溶液对采油残余油的作用机理研究 总被引:6,自引:0,他引:6
通过实验测定了HPAM溶液和黄原胶溶液的流变性、在多孔介质中的流变性和残余阻力系数 ,计算了衰竭层效应 .用不同的浓度和注入速度进行了驱油实验 .提出聚合物分子缠结作用的增强不仅引起表观粘度增加或衰竭层厚度降低 ,而且使平行于油水界面的拉动残余油的力增加 ,从而使残余油饱和度降低 ,采收率提高 .随浓度增加 ,HPAM溶液的表观粘度和残余阻力系数增加 ,衰竭层厚度减小 ;黄原胶溶液的浓度高于缠结浓度时 ,衰竭层厚度和表观粘度变化不大 .注入速度增加时 ,两种聚合物溶液的衰竭层厚度均降低 ,HPAM溶液的残余阻力系数不变 ,粘弹性增加 ;而黄原胶溶液的残余阻力系数下降 .不同浓度和注入速度情况下两种聚合物溶液的驱油结果证实了文中提出的聚合物分子缠结作用和衰竭层效应对残余油的作用机理 .分子结构的不同是造成两种聚合物溶液在多孔介质中渗流规律和对残余油作用机理的差别的根本原因 . 相似文献
80.
In developing a method for possible low level isotopic enrichment, which uses to advantage the equilibrium isotope effect
observed during U(1V)-U(VI) electron exchange reaction in sulphate solutions, details of a solvent extraction process involving
high concentration of a mixture of U(IV) and U(VI) and at low acid concentrations, are described. The extraction behaviour
of uranium under these conditions is discussed. During the extraction with amines, U(IV) tended to get oxidised in sulphate
solutions. 相似文献