全文获取类型
收费全文 | 1413篇 |
免费 | 68篇 |
国内免费 | 207篇 |
专业分类
化学 | 1495篇 |
晶体学 | 6篇 |
力学 | 6篇 |
综合类 | 1篇 |
数学 | 2篇 |
物理学 | 178篇 |
出版年
2024年 | 4篇 |
2023年 | 30篇 |
2022年 | 27篇 |
2021年 | 24篇 |
2020年 | 28篇 |
2019年 | 19篇 |
2018年 | 25篇 |
2017年 | 37篇 |
2016年 | 35篇 |
2015年 | 42篇 |
2014年 | 56篇 |
2013年 | 90篇 |
2012年 | 75篇 |
2011年 | 74篇 |
2010年 | 73篇 |
2009年 | 108篇 |
2008年 | 100篇 |
2007年 | 118篇 |
2006年 | 88篇 |
2005年 | 87篇 |
2004年 | 66篇 |
2003年 | 38篇 |
2002年 | 31篇 |
2001年 | 39篇 |
2000年 | 33篇 |
1999年 | 23篇 |
1998年 | 24篇 |
1997年 | 19篇 |
1996年 | 18篇 |
1995年 | 32篇 |
1994年 | 25篇 |
1993年 | 21篇 |
1992年 | 23篇 |
1991年 | 18篇 |
1990年 | 11篇 |
1989年 | 18篇 |
1988年 | 18篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 9篇 |
1984年 | 20篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1973年 | 3篇 |
排序方式: 共有1688条查询结果,搜索用时 15 毫秒
51.
Natalini B Marinozzi M Sardella R Macchiarulo A Pellicciari R 《Journal of chromatography. A》2004,1033(2):363-367
The chromatographic resolution of enantiomeric amino acids is accomplished on a reversed phase column using aqueous mobile phase containing the chiral reagent N,N-dimethyl-S-phenylalanine-Cu(II). The separation is a result of the whole interaction between the diastereomeric complex surface and the mixed stationary phase realized by the dynamic coating of the RP-18 carbon chains layer. The elution order seems to be related to the different water coordination capability on copper ion in the formation of the mixed ternary complexes. 相似文献
52.
Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature. 相似文献
53.
Effect of 1,10-phenanthroline on the extraction and separation of lithium(I), sodium(I) and potassium(I) with thenoyltrifluoroacetone 总被引:1,自引:0,他引:1
The extraction of Li+ with thenoyltrifluoroacetone (Htta) in the presence of 1,10-phenanthroline (phen) has been studied in various organic solvents. The remarkable enhancement of the extraction of Li+, that is a synergistic effect, was observed by the addition of phen, and the high extractability of Li+ was attained in toluene, benzene, chlorobenzene and o-dichlorobenzene. The extraction equilibrium of Li+, Na+ and K+ (denoted as M+) in the presence or absence of phen in chlorobenzene and the adduct formation reaction in the organic phase were studied in detail. The adduct of Li+ was Li(tta)(phen) in the wide concentration range of phen in the organic phase, while in Na+ and K+ M(tta)(phen)2 also exists in the high concentration region. The maximum value of the separation factor between Li+ and Na+ was observed in the present system and was larger than that in the Htta-trioctylphosphine oxide (TOPO)-benzene system reported previously. 相似文献
54.
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
55.
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
56.
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
57.
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
58.
59.
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
60.
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