全文获取类型
收费全文 | 804篇 |
免费 | 37篇 |
国内免费 | 8篇 |
专业分类
化学 | 722篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 61篇 |
物理学 | 61篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 35篇 |
2021年 | 44篇 |
2020年 | 33篇 |
2019年 | 27篇 |
2018年 | 22篇 |
2017年 | 14篇 |
2016年 | 24篇 |
2015年 | 23篇 |
2014年 | 30篇 |
2013年 | 46篇 |
2012年 | 54篇 |
2011年 | 55篇 |
2010年 | 52篇 |
2009年 | 39篇 |
2008年 | 50篇 |
2007年 | 53篇 |
2006年 | 41篇 |
2005年 | 53篇 |
2004年 | 35篇 |
2003年 | 26篇 |
2002年 | 22篇 |
2001年 | 6篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有849条查询结果,搜索用时 15 毫秒
151.
Mauricio Gomes Constantino Kleber Thiago de OliveiraAdilson Beatriz Gil Valdo José da Silva 《Tetrahedron letters》2003,44(13):2641-2643
A synthesis of a functionalized bicyclo[6.2.1]undecane, N-(7-hydroxymethyl-bicyclo[6.2.1]undeca-3,5,9-trien-2-yl)-4-methyl-benzenesulfonamide, is described. Starting with a [6+4] cycloaddition between cyclopentadiene and cycloheptatrienone, the final product was prepared in five steps with an overall 37% yield. The remarkable resistance to hydrolysis of an intermediate lactam was overcome by tosylating the amide and reducing with LiAlH4. 相似文献
152.
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
153.
Micelle‐Triggered β‐Hairpin to α‐Helix Transition in a 14‐Residue Peptide from a Choline‐Binding Repeat of the Pneumococcal Autolysin LytA
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Héctor Zamora‐Carreras Dr. Beatriz Maestro Dr. Erik Strandberg Prof. Anne S. Ulrich Dr. Jesús M. Sanz Dr. M. Ángeles Jiménez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8076-8089
Choline‐binding modules (CBMs) have a ββ‐solenoid structure composed of choline‐binding repeats (CBR), which consist of a β‐hairpin followed by a short linker. To find minimal peptides that are able to maintain the CBR native structure and to evaluate their remaining choline‐binding ability, we have analysed the third β‐hairpin of the CBM from the pneumococcal LytA autolysin. Circular dichroism and NMR data reveal that this peptide forms a highly stable native‐like β‐hairpin both in aqueous solution and in the presence of trifluoroethanol, but, strikingly, the peptide structure is a stable amphipathic α‐helix in both zwitterionic (dodecylphosphocholine) and anionic (sodium dodecylsulfate) detergent micelles, as well as in small unilamellar vesicles. This β‐hairpin to α‐helix conversion is reversible. Given that the β‐hairpin and α‐helix differ greatly in the distribution of hydrophobic and hydrophilic side chains, we propose that the amphipathicity is a requirement for a peptide structure to interact and to be stable in micelles or lipid vesicles. To our knowledge, this “chameleonic” behaviour is the only described case of a micelle‐induced structural transition between two ordered peptide structures. 相似文献
154.
155.
Beatriz Margolis 《Numerical Functional Analysis & Optimization》2013,34(5-6):577-588
We develop a calculus structure in the Banach lattice introduced in a preceding paper, having in mind an approximation problem appearing in non-smooth optimization. We show that the essential results depend as much on the order structure as on the analytical one. 相似文献
156.
157.
158.
159.
Dr. Iván Torres-Moya Carlos Benitez-Martin Beatriz Donoso Carlos Tardío Raúl Martín Dr. José R. Carrillo Prof. Dr. Ángel Díaz-Ortiz Dr. Francisco Najera Dr. Pilar Prieto Prof. Dr. Ezequiel Perez-Inestrosa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15572-15579
A series of donor–π–acceptor–π–donor (D -π-A-π-D) benzoazole dyes with 2H-benzo[d][1,2,3]triazole or BTD cores have been prepared and their photophysical properties characterized. The properties of these compounds display remarkable differences, mainly as a result of the electron-donor substituent. Dyes with the best properties have visible-light absorption over λ=400 nm, large Stokes shifts in the range of about 3500–6400 cm−1, and good fluorescence emission with quantum yields of up to 0.78. The two-photon absorption properties were also studied to establish the relationship between structure and properties in the different compounds synthesized. These results provided cross sections of up to 1500 GM, with a predominance of S2←S0 transitions and a high charge-transfer character. Time-dependent DFT calculations supported the experimental results. 相似文献
160.
Eva Garrido Dr. María Alfonso Dr. Borja Díaz de Greñu Beatriz Lozano-Torres Dr. Margarita Parra Dr. Pablo Gaviña Dr. M. Dolores Marcos Prof. Ramón Martínez-Máñez Dr. Félix Sancenón 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(13):2813-2816
This work reports the synthesis, characterization, and sensing behavior of a hybrid nanodevice for the detection of the potent abuse drug 25I-NBOMe. The system is based on mesoporous silica nanoparticles, loaded with a fluorescent dye, functionalized with a serotonin derivative and capped with the 5-HT2A receptor antibody. In the presence of 25I-NBOMe the capping antibody is displaced, leading to pore opening and rhodamine B release. This delivery was ascribed to 5-HT2A receptor antibody detachment from the surface due to its stronger coordination with 25I-NBOMe present in the solution. The prepared nanodevice allowed the sensitive (limit of detection of 0.6 μm ) and selective recognition of the 25I-NBOMe drug (cocaine, heroin, mescaline, lysergic acid diethylamide, MDMA, and morphine were unable to induce pore opening and rhodamine B release). This nanodevice acts as a highly sensitive and selective fluorometric probe for the 25I-NBOMe illicit drug in artificial saliva and in sweets. 相似文献