全文获取类型
收费全文 | 4703篇 |
免费 | 121篇 |
国内免费 | 29篇 |
专业分类
化学 | 3072篇 |
晶体学 | 15篇 |
力学 | 218篇 |
数学 | 787篇 |
物理学 | 761篇 |
出版年
2023年 | 21篇 |
2022年 | 74篇 |
2021年 | 74篇 |
2020年 | 63篇 |
2019年 | 71篇 |
2018年 | 57篇 |
2017年 | 59篇 |
2016年 | 130篇 |
2015年 | 115篇 |
2014年 | 146篇 |
2013年 | 256篇 |
2012年 | 327篇 |
2011年 | 388篇 |
2010年 | 203篇 |
2009年 | 212篇 |
2008年 | 272篇 |
2007年 | 279篇 |
2006年 | 301篇 |
2005年 | 285篇 |
2004年 | 228篇 |
2003年 | 220篇 |
2002年 | 201篇 |
2001年 | 67篇 |
2000年 | 70篇 |
1999年 | 47篇 |
1998年 | 61篇 |
1997年 | 66篇 |
1996年 | 63篇 |
1995年 | 44篇 |
1994年 | 53篇 |
1993年 | 35篇 |
1992年 | 27篇 |
1991年 | 24篇 |
1990年 | 22篇 |
1989年 | 17篇 |
1988年 | 20篇 |
1987年 | 16篇 |
1986年 | 11篇 |
1985年 | 25篇 |
1984年 | 20篇 |
1983年 | 12篇 |
1982年 | 16篇 |
1981年 | 12篇 |
1980年 | 20篇 |
1979年 | 22篇 |
1978年 | 17篇 |
1977年 | 11篇 |
1976年 | 14篇 |
1975年 | 11篇 |
1974年 | 9篇 |
排序方式: 共有4853条查询结果,搜索用时 15 毫秒
121.
Our recent developments concerning the fabrication of polymer microchips and their applications for biochemical analyses are reviewed. We first describe two methods of fabrication of polymer microfluidic chips, namely UV-laser photoablation and plasma etching that are well suited for the prototyping and mass fabrication of microchannel networks with integrated microelectrodes. These microanalytical systems can be coupled with various detection means including mass spectrometry, and their applications in capillary electrophoresis are presented here. We also present how UV laser photoablation can be used for the patterning of biomolecules on polymer surfaces for generating two-dimensional arrays of microspots to carry out affinity assays. Finally, the use of the microchips for the development of fast affinity and immunological assays with electrochemical detection is presented, demonstrating the potential of these polymer microchips for medical diagnostics and drug discovery. 相似文献
122.
123.
124.
Guilhem Godeau Christophe Brun Hélène Arnion Cathy Staedel Philippe Barthélémy 《Tetrahedron letters》2010,51(7):1012-1015
The synthesis of two novel glycosyl-nucleoside fluorinated amphiphiles (GNFs) derived from the 2H,2H,3H,3H-perfluoro-undecanoyl hydrophobic chain is described. The GNF amphiphiles, which feature either β-d-glucopyranosyl or β-d-lactopyranosyl moieties linked to a thymine base via a 1,2,3 triazole linker, were prepared using a ‘double click’ chemistry route. Surface tension measurements, gelation properties, and TEM studies show that GNFs spontaneously assemble into supramolecular structures. Similarly to their hydrocarbon analogues (GNLs), the GNFs have unique gelation properties in water. A minimum hydrogelation concentration of 0.1% (w/w), was determined in the case of the β-d-glucopyranosyl derivative. Cell viability studies indicate that fluorocarbon GNF 5 was not toxic for human cells (Huh7), whereas hydrocarbon analogue GNL is toxic above 100 μm. 相似文献
125.
126.
The Cr 2p and O 1s binding energy (BE) levels have been calculated by first principles methods for different models of hydroxylated (0001)-Cr2O3 surfaces. Several surface terminations have been considered. The calculations allow us to reproduce the O 1s shifts between O in oxide and OH groups. It is found that two main effects account for the OH binding energy shifts. On the one hand, the increased covalency of the O–H bond with respect to the Cr–O bond, lowers the electronic O (1s and 2p) energy, and in consequence the BE of the core levels (O 1s) are higher. On the other hand, the lower the OH coordination number, the higher the valence and core levels energy, and the lower the BE. Consequently, mono-coordinated hydroxyls have a binding energy near that of O2? in the oxide (ΔBEOH–O = ? 0.2–0.0 eV). Two-fold coordinated hydroxyls have a slightly higher BE (ΔBEOH–O = + 0.3 eV). Three-fold coordinated OH groups have a higher binding energy (ΔBEOH–O = + 0.6?0.7 eV), corresponding to that experimentally measured for OH groups. Finally, water adsorbed above OH groups exhibits a still higher BE (ΔBEHOH–O = + 0.9–1.0 eV). The ΔBE are slightly under-estimated under the initial state approximation, and overestimated under the final state (Z + 1) approximation. 相似文献
127.
Stefano Caramori Dr. Jérôme Husson Dr. Marc Beley Prof. Carlo A. Bignozzi Prof. Roberto Argazzi Dr. Philippe C. Gros Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(8):2611-2618
Mixtures of polypyridine FeII and CoII complexes are used as electron mediators in Ru–thienyltpy‐sensitised solar cells (tpy=terpyridine). The use of the metalorganic redox couples allows for improved charge‐collection efficiency with respect to the classical iodide/iodine couple which, when associated to Ru–tpy2 dyes, usually produces poor performance. The improved charge collection is explained by a combination of effective dye regeneration and decreased recombination with the oxidised electrolyte on the basis of data obtained by transient spectroscopy and photoelectrochemical measurements. The efficiency of the regeneration cascade is also critically dependent upon the ability of the CoII complex to intercept FeIII centres, as clearly indicated by chronocoulometry experiments. 相似文献
128.
The context of molecular structronics (from “molecular structure” and “electronics”) is that of molecular-level electrochemical storage of energy of sustainable origin (wind, solar). Due to its discontinuous availability, storage of this energy is a key issue. The targeted type of storage relies on implementing “electron reservoirs” within the structronic molecules by electrochemically forming dedicated chemical bonds according to non-catalytic processes. Reservoir bonds are therefore integral parts of the molecular backbone of structronic assemblies. When filled, electron reservoirs manifest themselves in the form of elongated covalent bonds that are to be cleaved for electron releasing (discharging) on demand. The scope of this short review is limited to pyridinium electrophores as particularly suited building blocks for the development of structronics. 相似文献
129.
Dr. Yoko Hasegawa Dr. Thomas Cantin Dr. Jonathan Decaens Dr. Samuel Couve-Bonnaire Prof. Dr. André B. Charette Prof. Dr. Thomas Poisson Prof. Dr. Philippe Jubault 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201438
The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh2((S)-TCPTAD)4 or Rh2((R)-BTPCP)4 catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r. 相似文献
130.
Dr. Thi Minh Thi Le Dr. Thibaud Brégent Prof. Dr. Philippe Jubault Prof. Dr. Thomas Poisson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(52):e202201514
Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH3CN under irradiation at 405 nm allowed the interconversion of the E-isomers into the Z-congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism. 相似文献