全文获取类型
收费全文 | 1298篇 |
免费 | 28篇 |
国内免费 | 3篇 |
专业分类
化学 | 763篇 |
晶体学 | 12篇 |
力学 | 30篇 |
数学 | 156篇 |
物理学 | 368篇 |
出版年
2023年 | 5篇 |
2022年 | 26篇 |
2021年 | 21篇 |
2020年 | 26篇 |
2019年 | 24篇 |
2018年 | 23篇 |
2017年 | 15篇 |
2016年 | 46篇 |
2015年 | 30篇 |
2014年 | 39篇 |
2013年 | 80篇 |
2012年 | 78篇 |
2011年 | 65篇 |
2010年 | 63篇 |
2009年 | 50篇 |
2008年 | 71篇 |
2007年 | 61篇 |
2006年 | 86篇 |
2005年 | 66篇 |
2004年 | 46篇 |
2003年 | 42篇 |
2002年 | 47篇 |
2001年 | 28篇 |
2000年 | 23篇 |
1999年 | 17篇 |
1998年 | 15篇 |
1997年 | 21篇 |
1996年 | 18篇 |
1995年 | 11篇 |
1994年 | 21篇 |
1993年 | 21篇 |
1992年 | 15篇 |
1991年 | 7篇 |
1990年 | 15篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 12篇 |
1984年 | 15篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1979年 | 6篇 |
1978年 | 8篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1973年 | 4篇 |
1972年 | 4篇 |
1968年 | 2篇 |
排序方式: 共有1329条查询结果,搜索用时 15 毫秒
71.
Klapars A Waldman JH Campos KR Jensen MS McLaughlin M Chung JY Cvetovich RJ Chen CY 《The Journal of organic chemistry》2005,70(24):10186-10189
[reaction: see text] A mild and transition-metal-free method for the alpha-arylation of aliphatic nitriles with activated heteroaryl halides was developed using NaHMDS or KHMDS as base at ambient temperature. The key to the success of this method is generation of the nitrile anion in the presence of the heteroaryl halide. The method is applicable to both primary and secondary carbonitriles and a wide range of heteroaryl halides. Selective monoarylation was observed with primary carbonitriles. The operational simplicity and the mild reaction conditions add to the value of this method as a practical alternative to the preparation of alpha-heteroaryl carbonitriles. 相似文献
72.
73.
Thomas Bridge Saher A. Shaikh Paul Thomas Joaquin Botta Peter J. McCormick Amit Sachdeva 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(50):18154-18161
Antibodies have found applications in several fields, including, medicine, diagnostics, and nanotechnology, yet methods to modulate antibody–antigen binding using an external agent remain limited. Here, we have developed photoactive antibody fragments by genetic site‐specific replacement of single tyrosine residues with photocaged tyrosine, in an antibody fragment, 7D12. A simple and robust assay is adopted to evaluate the light‐mediated binding of 7D12 mutants to its target, epidermal growth factor receptor (EGFR), on the surface of cancer cells. Presence of photocaged tyrosine reduces 7D12‐EGFR binding affinity by over 20‐fold in two out of three 7D12 mutants studied, and binding is restored upon exposure to 365 nm light. Molecular dynamics simulations explain the difference in effect of photocaging on 7D12‐EGFR interaction among the mutants. Finally, we demonstrate the application of photoactive antibodies in delivering fluorophores to EGFR‐positive live cancer cells in a light‐dependent manner. 相似文献
74.
Jorge‐Aarn Rangel‐Mndez Manlio‐Joaquin Graniel‐Sabido Juan‐Francisco Snchez‐Cruz Rosa Moo‐Puc 《Biomedical chromatography : BMC》2019,33(4)
To date, several methods for the quantification of tamoxifen and its metabolites have been developed, most of which employ liquid chromatography tandem–mass spectrometry (LC–MS/MS). These methods are highly sensitive and reproducible, but are also time‐consuming and require expensive equipment; one of their main disadvantages is matrix ionization effects. A more viable option, particularly in developing countries, is high‐performance liquid chromatography coupled with UV or fluorescence detection. We developed and validated a method for simultaneous quantification of tamoxifen, endoxifen and 4‐hydroxytamoxifen based on high‐performance liquid chromatography with fluorescence detection in a reverse‐phase column. The method is rapid (16 min plus 5 min of column re‐equilibrium), accurate (80–100%) and precise (0.23–6.00%), and does not require any additional irradiation process. Sample pretreatment consists of protein precipitation with acetonitrile under alkaline conditions, employing only 200 μL plasma. The validated method's wide range allowed quantification of steady‐state levels in patients under standard tamoxifen treatment (20 mg/day). This assay is ready for application in clinical studies and routine quantification of tamoxifen, endoxifen and 4‐hydroxytamoxifen in healthcare institutions. 相似文献
75.
Juliana Vaz Bevilaqua Lidia M. Lima Aline Gomes Cunha Eliezer J. Barreiro Tito L. M. Alves Lucia Moreira Campos Paiva Denise M.Guimarães Freire 《Applied biochemistry and biotechnology》2005,121(1-3):117-128
The last step of the production of four phthalimide-derived acids, designed to act as antiasthma drugs, was performed by enzymatic hydrolysis of the respective methyl or ethyl esters. The esters 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic methyl ester (PHT-MET), 4-ethyl-[2-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)]-phenoxyacetic ethyl ester, 4-(1,3-dioxo-1,3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester, and 2-(1,3-dioxo-1, 3-dihydro-2-isoindoylyl)-phenoxyacetic ethyl ester were hydrolyzed by immobilized lipase. The enzymatic reaction could be used only to produce the desired 4-substituted compounds. The best result that was found to hydrolysis of PHT-MET, and, therefore, that ester was selected for optimization experiments in a three-phase system. Reactions were performed with solid biocatalyst (Lipozyme® RM IM), organic solvent phase (ethyl acetate), and aqueous phase (saturated Na2CO3 solution). To optimize the reaction conditions, an experimental design optimization procedure was used. The variables studied were the amount of enzyme, the temperature, and the volume of the aqueous solution. Time course experiments were then performed for different initial enzyme concentrations (0.5, 0.9, and 1.4 UH/mL of solvent). The optimized reaction conditions found were 20 mg of Lipozyme (0.9 UH/mLsolvent) and 5.0 mL of Na2CO3(sat) at 40°C for 6 h. 相似文献
76.
Ana Elisa Ferreira Oliveira Arnaldo César Pereira Mayra Asevedo Campos de Resende Lucas Franco Ferreira 《Electroanalysis》2022,34(5):809-819
In this work, a silver/silver chloride ink is fabricated using two steps. First the silver ink is prepare using silver, nail polish and acetone. Then the silver ink is painted in a paper substrate and a silver chloride layer is deposited using a bleach solution. The result is the silver/silver chloride conductive ink. The silver ink is cheap ($2.49/g), well-dispersive and very easy to fabricate. The materials were characterized by SEM and XRD. The Ag ink showed the formation of a continuous network throughout the silver ink film with fewer agglomeration. The effective chlorination process was also observed in the Ag/AgCl characterization. Since the Ag/AgCl substrate will be used as a quasi-reference electrode, it is important to investigate the electrical properties. The Ag ink showed an average ohmic resistance of 2.27 Ω. The addition of the AgCl layer decreases the conductivity, as expected. In summary, the Ag/Ag/Cl ink developed is simple, well-dispersed, cheap and with good conductivity. Therefore, it can be used as a conductive ink in the fabrication of quasi-reference electrodes. 相似文献
77.
Patrícia Homobono Brito de Moura Wolfgang Brandt Andrea Porzel Roberto Carlos Campos Martins Ivana Correa Ramos Leal Ludger A. Wessjohann 《Molecules (Basel, Switzerland)》2022,27(8)
A rare dihydoxyflavan-epicatechin proanthocyanidin, entcassiflavan-(4β→8)-epicatechin, was isolated from Dalbergia monetaria, a plant widely used by traditional people from the Amazon to treat urinary tract infections. The constitution and relative configuration of the compound were elucidated by HR-MS and detailed 1D- and 2D-NMR measurements. By comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD spectra of all 16 possible isomers, the absolute configuration, the interflavan linkage, and the atropisomers could be determined. 相似文献
78.
Peralta Cecilia Mariana Acosta Gimena Henestrosa Cecilia Gil Raúl Andrés Fernández Liliana Patricia 《Journal of Analytical Chemistry》2022,77(3):308-317
Journal of Analytical Chemistry - The present development involved a flow injection strategy using a mini-column of multiwalled carbon nanotubes and fluorescent detection (λex of 283 nm,... 相似文献
79.
Motta Neves Roberta Ornaghi Heitor Luiz Duchemin Benoit Zattera Ademir Jos Campos Amico Sandro 《Cellulose (London, England)》2022,29(6):3209-3224
Cellulose - Microcrystalline cellulose (MCC) has unique properties and its use as reinforcement for polymer composites has been increasing. However, the intrinsic incompatibility with most polymers... 相似文献
80.
Dayanne Cristiane Mozaner Bordin Marcela Nogueira Rabelo Alves Eduardo Geraldo de Campos Bruno Spinosa De Martinis 《Journal of separation science》2016,39(6):1168-1172
Disposable pipette tips extraction consists of a solid‐phase extraction in which the sorbent is poorly dispersed in a pipette tip, which allows a quick and dynamic contact between the aspirated analyte from the sample and the solid phase. It is a technique used particularly in food and forensic analysis, since it requires a small amount of sample and solvent. This article highlights the principles, advantages and disadvantages of the disposable pipette tips extraction method and reviews recent applications. 相似文献