全文获取类型
收费全文 | 38021篇 |
免费 | 1108篇 |
国内免费 | 305篇 |
专业分类
化学 | 25958篇 |
晶体学 | 219篇 |
力学 | 866篇 |
综合类 | 1篇 |
数学 | 6801篇 |
物理学 | 5589篇 |
出版年
2023年 | 160篇 |
2021年 | 352篇 |
2020年 | 497篇 |
2019年 | 457篇 |
2018年 | 393篇 |
2017年 | 396篇 |
2016年 | 812篇 |
2015年 | 837篇 |
2014年 | 927篇 |
2013年 | 1895篇 |
2012年 | 2049篇 |
2011年 | 2531篇 |
2010年 | 1360篇 |
2009年 | 1161篇 |
2008年 | 2208篇 |
2007年 | 2210篇 |
2006年 | 2331篇 |
2005年 | 2189篇 |
2004年 | 2016篇 |
2003年 | 1667篇 |
2002年 | 1578篇 |
2001年 | 404篇 |
2000年 | 345篇 |
1999年 | 316篇 |
1998年 | 311篇 |
1997年 | 505篇 |
1996年 | 470篇 |
1995年 | 427篇 |
1994年 | 473篇 |
1993年 | 441篇 |
1992年 | 382篇 |
1991年 | 375篇 |
1990年 | 317篇 |
1989年 | 327篇 |
1988年 | 303篇 |
1987年 | 270篇 |
1986年 | 286篇 |
1985年 | 444篇 |
1984年 | 454篇 |
1983年 | 367篇 |
1982年 | 412篇 |
1981年 | 392篇 |
1980年 | 416篇 |
1979年 | 330篇 |
1978年 | 345篇 |
1977年 | 317篇 |
1976年 | 255篇 |
1975年 | 227篇 |
1974年 | 222篇 |
1973年 | 190篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
2.
A CE instrument that can be assembled from commercially available components with minimal construction effort is described. Except for the electronic control circuitry no specially made parts are required. It is based on a flexible design of microfluidic, electropneumatic, and electronic sections and different configurations can easily be implemented. Automated injection into the capillary is performed hydrodynamically by the application of a pressure for a controlled length of time. The performance of the device was tested with a contactless conductivity detector by separating different metal ions. In addition, nine metal cations related to the quality of honey were separated in 2.3 min and four honey samples were analysed quantitatively to demonstrate the applicability of the method. 相似文献
3.
Ein elektronenreiches cyclisches (Alkyl)(amino)carben auf Au(111)-, Ag(111)- und Cu(111)-Oberflächen
Anne Bakker Dr. Matthias Freitag Elena Kolodzeiski Peter Bellotti Dr. Alexander Timmer Dr. Jindong Ren Bertram Schulze Lammers Daniel Moock Prof. Dr. Herbert W. Roesky Dr. Harry Mönig Dr. Saeed Amirjalayer Prof. Dr. Harald Fuchs Prof. Dr. Frank Glorius 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13745-13749
4.
Peter T. Smith Younghoon Kim Dr. Bahiru Punja Benke Prof. Kimoon Kim Prof. Christopher J. Chang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4932-4937
We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications. 相似文献
5.
Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
6.
7.
The kinetics of the dissipation of chlortetracycline in the aquatic environment was studied over a period of 90 days using microcosm experiments and distilled water controls. The distilled water control experiments, carried out under dark conditions as well as exposed to natural sunlight, exhibited biphasic linear rates of dissipation. The microcosm experiments exhibited triphasic linear rates of degradation both in the water phase (2.7 × 10−2, 7 × 10−3, 1.3 × 10−3 μg g−1 day–1) and the sediment phase (3.4 × 10−2, 6 × 10−3, 1 × 10−3 μg g−1 day–1). The initial slow rate of dissipation in the dark control (3 × 10−3 μg g−1 day–1) was attributed to a combination of evaporation and hydrolysis, whereas the subsequent fast rate (1.8 × 10−3 μg g−1 day–1) was attributed to a combination of evaporation, hydrolysis, and microbial degradation. For the sunlight-exposed control, the initial slow rate of dissipation (1.5 × 10−3 μg g−1 day–1) was attributed to a combination of evaporation, hydrolysis, and photolysis, whereas the subsequent fast rate was attributed to a combination of evaporation, hydrolysis, photolysis, and microbial degradation (5.1 × 10−3 μg g−1 day–1). The initial fast rate of dissipation in the water phase of the microcosm experiment is attributed to a combination of evaporation, hydrolysis, photolysis, and microbial degradation, whereas all subsequent slow rates in the water phase and all rates of degradation in the sediment phase are attributed to microbial degradation of the colloidal and sediment particle adsorbed antibiotic. A multiphase zero-order kinetic model is presented that takes into account (a) dissipation of the antibiotic via evaporation, hydrolysis, photolysis, microbial degradation, and adsorption by colloidal and sediment particles and (b) the dependence of the dissipation rate on the concentration of the antibiotic, type and count of microorganisms, and type and concentration of colloidal particles and sediment particle adsorption sites within a given aquatic environment. 相似文献
8.
The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs () routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes. 相似文献
9.
10.