全文获取类型
收费全文 | 3847篇 |
免费 | 183篇 |
国内免费 | 307篇 |
专业分类
化学 | 3904篇 |
晶体学 | 15篇 |
力学 | 5篇 |
综合类 | 1篇 |
数学 | 20篇 |
物理学 | 392篇 |
出版年
2024年 | 14篇 |
2023年 | 94篇 |
2022年 | 24篇 |
2021年 | 46篇 |
2020年 | 43篇 |
2019年 | 93篇 |
2018年 | 74篇 |
2017年 | 86篇 |
2016年 | 100篇 |
2015年 | 118篇 |
2014年 | 165篇 |
2013年 | 234篇 |
2012年 | 173篇 |
2011年 | 247篇 |
2010年 | 221篇 |
2009年 | 272篇 |
2008年 | 234篇 |
2007年 | 280篇 |
2006年 | 288篇 |
2005年 | 314篇 |
2004年 | 293篇 |
2003年 | 165篇 |
2002年 | 107篇 |
2001年 | 84篇 |
2000年 | 80篇 |
1999年 | 59篇 |
1998年 | 57篇 |
1997年 | 57篇 |
1996年 | 52篇 |
1995年 | 49篇 |
1994年 | 30篇 |
1993年 | 30篇 |
1992年 | 25篇 |
1991年 | 27篇 |
1990年 | 27篇 |
1989年 | 9篇 |
1988年 | 15篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 3篇 |
1984年 | 9篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有4337条查询结果,搜索用时 31 毫秒
61.
62.
63.
The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect
of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated.
It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7.
The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7. 相似文献
64.
Raffaello Lazzaroni Roberta Settambolo Giuditta Guazzelli 《Journal of organometallic chemistry》2007,692(9):1812-1816
We review our recent results on the rhodium-catalyzed hydroformylation of chiral and prochiral N-allylpyrroles as a synthetic route to stereodefined 5,6-dihydro- and 5,6,7,8-tetrahydroindolizines. The indolizine nucleus at different degrees of unsaturation is a building block of natural and synthetic target compounds; thus new approaches, especially if stereoselective and/or stereospecific, are highly desirable. The construction of the indolizine architectures reported here occurs by formation of a C8-C9 bond through intramolecular cyclization of the 4-pyrrolylbutanal intermediate. 相似文献
65.
Yoshitane Imai Kakuhiro Kawaguchi Tomohiro Sato Michiya Fujiki Yoshio Matsubara 《Tetrahedron letters》2007,48(16):2927-2930
By using (1R,2R)-1,2-diphenylethylenediamine as a chiral molecule and 2-anthracenecarboxylic acid as a fluorescent molecule, we created a chiral supramolecular organic fluorophore having circularly polarized luminescence properties in the solid-state. 相似文献
66.
Antonio García Martínez Santiago de la Moya Cerero Beatriz Lora Maroto 《Tetrahedron》2005,61(12):3055-3064
An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed. 相似文献
67.
J. Sivaguru Hideaki Saito Thomas Poon Waldemar Adam Yoshihisa Inoue Nicholas J. Turro 《Tetrahedron》2006,62(28):6707-6717
On photooxygenation (methylene blue as sensitizer) of E/Z enecarbamates, equipped with the oxazolidinone chiral auxiliary, the oxidative cleavage of the alkenyl functionality releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense (R vs S) of the stereoselectivity in the MDB formation depends on the choice of the alkene configuration; the efficacy of stereocontrol may be tuned by appropriate solvent and temperature conditions. Highlighted is the finding that the formation of the preferred MDB enantiomer (R or S) depends for the E isomer on the chosen solvent and temperature, but not for the corresponding Z isomer. The activation parameters for the various solvents disclose that differential entropy effects (ΔΔS‡) dominate the conformationally more flexible E diastereomers. As mechanistic rationale for this unprecedented conformationally imposed stereochemical behavior, we propose the competitive action of stereoselective vibrational quenching of the attacking singlet oxygen by the enecarbamate versus sterically controlled stereoselective oxidative cleavage of its double bond. 相似文献
68.
Two molecular imprinting polymer (MIP) monolithic columns with (S)-(-)-1,1'-bi-2-naphthol and (R)-(+)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol as the templating molecules, respectively, have been prepared by in situ polymerization using 4-vinylpyridine and ethylene dimethacrylate as functional monomer and cross-linker, respectively. The columns with good flow-through properties were obtained by changing the molar ratio of the functional monomer and the template molecule. The effects of mobile-phase composition on separation of enantiomers were systematically investigated. The results indicate that hydrophobic interaction in aqueous solution and hydrogen-bonding interaction in ACN between the enantiomers and polymers could play important roles in the retention and resolution. The effects of chromatographic conditions, such as flow rate, column temperature, sample loading, on the enantioseparation were also studied. Further, these two MIP columns show a cross-reactivity. 相似文献
69.
Akinori Furutani 《Tetrahedron letters》2004,45(41):7621-7624
The diastereoselective [2+2] photocycloaddition of a cyclohexenonecarboxylate containing (−)-8-(4-nitrophenyl)menthyl as a chiral auxiliary to ethylene gave the photocycloadduct, a bicyclo[4.2.0]octanone derivative, with a high degree of diastereoselectivity. A photoreaction, conducted in CH2Cl2 at −78 °C gave the corresponding photocycloadduct in 88% de. In the presence of Ti(OR)4 or Me3SnCl, the diastereoselectivity was increased up to 92% de. 相似文献
70.
Q. Zhong L. He T. E. Beesley W. S. Trahanovsky P. Sun C. Wang D. W. Armstrong 《Chromatographia》2006,64(3-4):147-155
The comparisons of five different chiral stationary phases (CSPs) based on 2,6-dinitro-4-trifluoromethylphenyl (DNP-TFM) ether substituted β-cyclodextrin are presented. The five CSPs differ from each other in the linkage/spacer chemistry, or on the position of the substituents on β-cyclodextrin, or in the sequence of the synthetic procedure. The results show that there are two optimum combinations: (1) DNP-TFM randomly substituted on the β-cyclodextrin as the chiral selector along with a carbamate linkage chain bonding it to the silica support; and (2) β-cyclodextrin derivatized by DNP-TFM substituents only on the C-2 and C-3 positions of the cyclodextrin with an ether linkage chain anchoring it to the silica gel. These two combinations show complementary separations for some enantiomers. The spacer chain effect is much more pronounced for the CSP based on the β-cyclodextrin derivatives with DNP-TFM substituents only on C-2 and C-3 positions than its randomly substituted counterpart. The sequence of derivatizing the cyclodextrin and attaching it to silica gel also affects its selectivity and efficiency. The β-cyclodextrin should be derivatized before it is linked to the silica gel. 相似文献