全文获取类型
收费全文 | 1964篇 |
免费 | 324篇 |
国内免费 | 170篇 |
专业分类
化学 | 1356篇 |
晶体学 | 25篇 |
力学 | 144篇 |
综合类 | 12篇 |
数学 | 173篇 |
物理学 | 748篇 |
出版年
2024年 | 6篇 |
2023年 | 34篇 |
2022年 | 75篇 |
2021年 | 85篇 |
2020年 | 72篇 |
2019年 | 58篇 |
2018年 | 75篇 |
2017年 | 68篇 |
2016年 | 95篇 |
2015年 | 114篇 |
2014年 | 123篇 |
2013年 | 157篇 |
2012年 | 188篇 |
2011年 | 199篇 |
2010年 | 112篇 |
2009年 | 127篇 |
2008年 | 125篇 |
2007年 | 123篇 |
2006年 | 102篇 |
2005年 | 78篇 |
2004年 | 40篇 |
2003年 | 33篇 |
2002年 | 35篇 |
2001年 | 31篇 |
2000年 | 36篇 |
1999年 | 30篇 |
1998年 | 25篇 |
1997年 | 24篇 |
1996年 | 32篇 |
1995年 | 15篇 |
1994年 | 18篇 |
1993年 | 12篇 |
1992年 | 7篇 |
1991年 | 15篇 |
1990年 | 24篇 |
1989年 | 16篇 |
1988年 | 11篇 |
1987年 | 11篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1981年 | 2篇 |
1976年 | 2篇 |
1957年 | 1篇 |
1942年 | 1篇 |
1941年 | 1篇 |
1936年 | 4篇 |
1930年 | 2篇 |
1929年 | 1篇 |
1927年 | 1篇 |
1923年 | 1篇 |
排序方式: 共有2458条查询结果,搜索用时 15 毫秒
251.
Chen R Wang L Xiong C Zhou Y Zhen C Zhang N Tang Y Zhou X Wang J Nie Z Chen Y 《The Analyst》2011,136(18):3809-3814
Electrosonic spray ionization (ESSI) is a derivative technique of electrospray ionization (ESI) for mass spectrometry (MS) in which droplets are charged in the course of sonic spray. In this study, we applied ESSI MS to direct analysis of oligosaccharides and alpha hydroxy acids (AHAs) in fruits. The components were extracted from fruit fleshes by a feasible method prior to ESSI MS analysis, but the fruit juices were analyzed without further pretreatment. The results demonstrate that mainly alkali metal adducts of oligosaccharides are favorably produced in positive ion mode, while deprotonated AHAs and oligosaccharides are produced in negative ion mode. Compared with mass spectra obtained using electrospray droplet impact/secondary ion mass spectrometry (EDI/SIMS), mass spectra using ESSI make the identification of oligosaccharides more straightforward in positive ion mode than in negative ion mode. 相似文献
252.
A new disposable multi-walled carbon nanotubes modified single-sided heated screen-printed carbon electrode (MWNT/ss-HSPCE) was fabricated. The electrochemical behavior of silybin was investigated by cyclic voltammetry and the probable electrode reaction mechanism was proposed. A simple and cheap direct current heating supplier was used to heating the electrode for adsorptive accumulation of silybin. The square wave voltammetric stripping peak current of silybin at MWNT/ss-HSPCE with an elevated electrode temperature of 50 °C only during accumulation step was dramatically improved compared with that at bare single-sided heated screen-printed carbon electrode (ss-HSPCE) without heating. This enhancement was mainly contributed to the combination of the advantages of multi-walled carbon nanotubes and electrically heated electrodes. Under optimum conditions, two detection linear ranges of silybin were from 1.0 × 10−9 to 1.0 × 10−7 M and 3.0 × 10−7 to 1.0 × 10−6 M. A detection limit of 5.0 × 10−10 M could be obtained (S/N = 3), which was more than two magnitudes lower than that at bare ss-HSPCE without heating. To the best of our knowledge, this was also at least two magnitudes lower than any others for electrochemical detection of silybin in the literature. Finally, the method was successfully applied to the determination of silybin in pharmaceutical tablets. 相似文献
253.
254.
Organocatalytic asymmetric conjugate addition of α-nitroketones to β,γ-unsaturated α-keto esters has been developed. A pyrrolidine-based thiourea-tertiary amine was identified as the best catalyst. The reaction was found to proceed via cascade conjugate addition and acyl transfer reaction. A number of α-nitroketones and β,γ-unsaturated α-keto esters were examined in this transformation. 5-Nitro-2-acyloxypent-2-enoates were obtained in good yields (up to 99%) and enantioselectivities (up to 99% ee). The products could be hydrolyzed to provide 5-nitro-2-oxopentanoates, which are not available from the direct addition of nitromethane to β,γ-unsaturated α-keto esters. 相似文献
255.
Liu TL Ma H Zhang FG Zheng Y Nie J Ma JA 《Chemical communications (Cambridge, England)》2011,47(48):12873-12875
An efficient, catalytic, and enantioselective 1,2-addition of terminal 1,3-diynes to aromatic ketones was realized in the presence of 10 mol% of a Cu(OTf)(2)-hydroxycamphor-sulfonamide complex, affording chiral tertiary alcohols in up to 94% yield and 90% ee. 相似文献
256.
257.
258.
259.
Tumarkin E Nie Z Park JI Abolhasani M Greener J Sherwood-Lollar B Günther A Kumacheva E 《Lab on a chip》2011,11(20):3545-3550
We report a microfluidic (MF) approach to studies of temperature mediated carbon dioxide (CO(2)) transfer between the gas and the liquid phases. Micrometre-diameter CO(2) bubbles with a narrow size distribution were generated in an aqueous or organic liquid and subsequently were subjected to temperature changes in the downstream channel. In response to the cooling-heating-cooling cycle the bubbles underwent corresponding contraction-expansion-contraction transitions, which we term 'bubble breathing'. We examined temperature-controlled dissolution of CO(2) in four exemplary liquid systems: deionized water, a 0.7 M aqueous solution of NaCl, ocean water extracted from Bermuda coastal waters, and dimethyl ether of poly(ethylene glycol), a solvent used in industry for absorption of CO(2). The MF approach can be extended to studies of other gases with a distinct, temperature-dependent solubility in liquids. 相似文献
260.
The electronic coupling between two amine redox sites bridged through the 5,5′‐positions of the [Re(CO)3Cl]‐chelated 2,2′‐bipyridine was studied by the electrochemical, spectroscopic, and EPR analysis. Interestingly, multiple near‐infrared bands were observed in this new organic mixed‐valent system. The results are interpreted with the aid of DFT and TDDFT calculations. 相似文献