全文获取类型
收费全文 | 963篇 |
免费 | 125篇 |
国内免费 | 143篇 |
专业分类
化学 | 1026篇 |
晶体学 | 6篇 |
力学 | 14篇 |
综合类 | 1篇 |
物理学 | 184篇 |
出版年
2023年 | 2篇 |
2022年 | 7篇 |
2021年 | 18篇 |
2020年 | 45篇 |
2019年 | 19篇 |
2018年 | 24篇 |
2017年 | 25篇 |
2016年 | 39篇 |
2015年 | 32篇 |
2014年 | 44篇 |
2013年 | 73篇 |
2012年 | 56篇 |
2011年 | 53篇 |
2010年 | 58篇 |
2009年 | 80篇 |
2008年 | 83篇 |
2007年 | 88篇 |
2006年 | 81篇 |
2005年 | 85篇 |
2004年 | 79篇 |
2003年 | 59篇 |
2002年 | 41篇 |
2001年 | 26篇 |
2000年 | 22篇 |
1999年 | 22篇 |
1998年 | 12篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 9篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
排序方式: 共有1231条查询结果,搜索用时 296 毫秒
131.
Lechel T Gerhard M Trawny D Brusilowskij B Schefzig L Zimmer R Rabe JP Lentz D Schalley CA Reissig HU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(27):7480-7491
Lithiated alkoxyallenes, nitriles, and carboxylic acids have been employed as precursors in a three-component reaction leading to highly substituted β-alkoxy-β-ketoenamides. Upon treatment with trifluoroacetic acid, these enamides could be easily cyclized to 5-acetyloxazole derivatives. The synthesis is very flexible with respect to the substitution pattern at C-2 and C-4 of the oxazole core. A mechanistic suggestion for the oxazole formation is presented on the basis of (18)O-labeled compounds and their mass spectrometric analysis. In several cases, 1,2-diketones are formed as side products or even as major components. The acetyl moiety at C-5 of the oxazole derivatives can efficiently be converted into alkenyl or alkynyl moieties, which allows a multitude of subsequent reactions. Condensation reactions of the acetyl group provided the expected oxime or hydrazone. By applying a Fischer reaction, the phenylhydrazone could be transferred into an indole, which emphasizes the potential of 5-acetyloxazoles for the preparation of highly substituted (poly)heterocyclic systems. The alkynyl group at C-2 is prone to addition reactions, providing an enamine with interesting photophysical properties. Sonogashira couplings were performed with 5-alkynyl-substituted oxazoles, furnishing the expected aryl-substituted products. This alkynyl unit was employed for the preparation of a new, star-shaped trisoxazole derivative. The ability of this multivalent compound to form self-assembled monolayers between the basal plane of highly oriented pyrolytic graphite and 1-phenyloctane was demonstrated by scanning tunneling microscopy (STM). The star-shaped compound seems to prefer the C(3)-symmetric arrangement in this two-dimensional crystal. Two 1,2-diketones were smoothly converted into functionalized quinoxaline derivatives. 相似文献
132.
In this work a novel unbreakable sol-gel-based in-tube device for on-line solid phase microextraction (SPME) was developed. The inner surface of a copper tube, intended to be used as a high performance liquid chromatography (HPLC) loop, was electrodeposited by metallic Cu followed by the self assembled monolayers (SAM) of 3-(mercaptopropyl) trimethoxysilane (3MPTMOS). Then, poly (ethyleneglycol) (PEG) was chemically bonded to the -OH sites of the SAM already covering the inner surface of the copper loop using sol-gel technology. The homogeneity and the porous surface structure of the SAM and sol-gel coatings were examined using the scanning electron microscopy (SEM) and adsorption/desorption porosimetry (BET). The prepared loop was used for online in-tube SPME (capillary microextraction) of some selected polycyclic aromatic hydrocarbons (PAHs), as model compounds, from the aquatic media. After extraction, the HPLC mobile phase was used for on-line desorption and elution of the extracted analytes from the loop to the HPLC column. Major parameters affecting the extraction efficiency including the sample flow rate through the copper tube, loading time, desorption time and sample volume were optimized. For investigating the sorbent efficiency, four loops based on the copper tube itself, the copper tube after electrodeposition with Cu and the tubes with the SAMs and SAMs-sol-gel coating were made and compared. The SAMs-sol-gel coated loop clearly shows a prominently lead of at least 20-100 times of higher efficiency. The linearity for the analytes was in the range of 0.01-500 μg L(-1). Limit of detection (LOD) was in the range of 0.005-0.5 μg L(-1) and the RSD% values (n=5) were all below 8.3% at the 5 μg L(-1) level. The developed method was successfully applied to real water samples while the relative recovery percentages obtained for the spiked water samples were from 90 to 104%. The prepared loop exhibited long life time due to its remarkable solvent and mechanical stability. Different solvents such as methanol, acetonitrile and acetone were passed through the loop for many days and it was also used for more than 100 extractions/desorption of the selected analytes and no decrease in the peak areas was observed. 相似文献
133.
Novoselov KS 《Angewandte Chemie (International ed. in English)》2011,50(31):6986-7002
Much like the world described in Abbott's "Flatland", graphene is a two-dimensional object. And, as "Flatland" is "A Romance of Many Dimensions", graphene is much more than just a flat crystal. It possesses a number of unusual properties which are often unique or superior to those in other materials. In this brief lecture I would like to explain the reason for my (and many other people's) fascination with this material, and invite the reader to share some of the excitement I've experienced while researching it. 相似文献
134.
135.
136.
137.
Anna Chachaj-Brekiesz Krzysztof Zborowski Joanna Zemła Katarzyna Makyła-Juzak 《Molecular physics》2013,111(24):3567-3577
Symmetrical triblock semifluorinated n-alkane, di(perfluorohexyl)hexane of the formula F(CF2)6(CH2)6(CF2)6F (abbreviated F6H6F6), has been synthesised and investigated at the air/water interface. Our results show for the first time that this unusual film-forming material, completely hydrophobic in nature and possessing no polar group, is capable of stable film formation at the free water surface. The surface pressure–area isotherm of the studied compound exhibited two regions: corresponding to monotonous pressure rise, followed by a pseudo-plateau region. Visualisation of film structure with Brewster angle microscope (BAM) proved the formation of domains within the pseudo-plateau region. A closer insight into the structure of these domains with atomic force microscope (AFM) proved their ordered, circular shape. The average area of F6H6F6 domain was found to depend on surface pressure value, as it is 4.98 ± 1.75 μm2 at π = 1.2 mN/m to 16.54 ± 0.31 μm2 at π = 1.7 mN/m. Following performed quantum-chemical calculations, it can be concluded that the observed surface aggregates from F6H6F6 are formed by linear conformers with shifted CF and CH parts. The calculated domain thickness is between 20 and 21 Å, which perfectly agrees with the experimental value estimated from AFM measurements (20.3 ± 1.4 Å). 相似文献
138.
139.
The phenothiazine derivatives, Toluidine Blue O and Azur A, and the phenoxazine derivative Nile Blue were bound covalently to self-assembled cystamine monolayers chemisorbed on gold electrodes by derivatization of the surface amino groups with two different bifunctional spacers: terephthaloyl chloride and 1,6-hexamethylene-diisocyanate.The formation of the amido- and urea-derivatives of the parent compounds after covalent immobilization induces a shift of their redox potentials towards more positive values which can easily be detected by cyclic voltammetry.UV-Vis difference spectroelectrochemistry has been used to characterize the electroactive species immobilized onto transparent gold electrode surfaces in both oxidation states. In every case, the oxidized-minus-reduced (and reduced-minus-oxidized) difference spectra of the immobilized redox species show a shift of the UV maxima towards longer wavelengths and a shift of the Vis maximum towards shorter wavelengths when compared with their parent compounds. Each redox species showed different optical characteristics depending on the spacer used for immobilization.For phenothiazine derivatives immobilized with 1,6-hexamethylene di-isocyanate the total surface coverages obtained by optical methods were close to those obtained by cyclic voltammetry. However, for the same derivatives immobilized with terephthaloyl chloride, and for Nile Blue, independently of the spacer used, higher surface coverages were found by optical methods than by cyclic voltammetry. 相似文献
140.