全文获取类型
收费全文 | 2953篇 |
免费 | 142篇 |
专业分类
化学 | 1819篇 |
晶体学 | 21篇 |
力学 | 47篇 |
数学 | 603篇 |
物理学 | 605篇 |
出版年
2021年 | 40篇 |
2020年 | 60篇 |
2019年 | 43篇 |
2018年 | 50篇 |
2017年 | 63篇 |
2016年 | 154篇 |
2015年 | 136篇 |
2014年 | 121篇 |
2013年 | 234篇 |
2012年 | 155篇 |
2011年 | 200篇 |
2010年 | 128篇 |
2009年 | 97篇 |
2008年 | 101篇 |
2007年 | 73篇 |
2006年 | 66篇 |
2005年 | 32篇 |
2004年 | 41篇 |
2003年 | 31篇 |
2002年 | 28篇 |
2001年 | 24篇 |
2000年 | 31篇 |
1999年 | 28篇 |
1998年 | 27篇 |
1997年 | 24篇 |
1990年 | 25篇 |
1988年 | 22篇 |
1987年 | 22篇 |
1986年 | 22篇 |
1985年 | 30篇 |
1984年 | 30篇 |
1983年 | 26篇 |
1982年 | 28篇 |
1981年 | 22篇 |
1978年 | 25篇 |
1977年 | 22篇 |
1976年 | 23篇 |
1973年 | 22篇 |
1969年 | 22篇 |
1968年 | 40篇 |
1966年 | 23篇 |
1965年 | 42篇 |
1964年 | 45篇 |
1963年 | 27篇 |
1962年 | 38篇 |
1961年 | 36篇 |
1960年 | 32篇 |
1959年 | 29篇 |
1958年 | 23篇 |
1957年 | 25篇 |
排序方式: 共有3095条查询结果,搜索用时 15 毫秒
101.
Veronika Pilařová Tomáš Gottvald Pavel Svoboda Ondřej Novák Karolína Benešová Sylvie Běláková Lucie Nováková 《Analytica chimica acta》2016
The goal of this study was to develop an effective supercritical fluid chromatography method using single quadrupole MS for analysis of all isomeric forms of vitamin E. Finally, two fast and effective methods, the high resolution one and the high speed one, for the determination of 8 vitamin E isomers in human serum were developed. 相似文献
102.
Jan Pecháček Jiří Václavík Jan Přech Petr Šot Jakub Januščák Beáta Vilhanová Jiří Vavřík Marek Kuzma Petr Kačer 《Tetrahedron: Asymmetry》2013,24(4):233-239
We present, to the best of our knowledge, the first parametric study of the asymmetric transfer hydrogenation of imines catalyzed by a Noyori-type catalytic complex based on ruthenium. A model imine for this study was 1-methyl-3,4-dihydroisoquinoline, and a well-known complex RuCl(η6-p-cymene)((1S,2S)-N-p-toluenesulfonyl-1,2-diphenylethylenediamine) was chosen as the model catalyst. The reactions were performed in the presence of a formic acid–triethylamine mixture as the source of hydrogen.The parameters examined include general parameters, for example, concentration, temperature, and substrate-to-catalyst molar ratio, as well as parameters specific to this particular reaction, such as the amount of the hydrogenation mixture used, the ratio of its components, or the inhibitive effect of carbon dioxide. During this study, several unexpected parameters worth further investigation have emerged. 相似文献
103.
Dr. Jan Vícha Dr. Petr Švec Dr. Zdeňka Růžičková Dr. Maksim A. Samsonov Kateřina Bártová Prof. Aleš Růžička Dr. Michal Straka Dr. Martin Dračínský 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(40):8698-8702
Spin-orbit (SO) heavy-atom on the light-atom (SO-HALA) effect is the largest relativistic effect caused by a heavy atom on its light-atom neighbors, leading, for example, to unexpected NMR chemical shifts of 1H, 13C, and 15N nuclei. In this study, a combined experimental and theoretical evidence for the SO-HALA effect transmitted through hydrogen bond is presented. Solid-state NMR data for a series of 4-dimethylaminopyridine salts containing I−, Br− and Cl− counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO-HALA effect through hydrogen bonds. 相似文献
104.
Is it true that every matching in the n-dimensional hypercube can be extended to a Gray code? More than two decades have passed since Ruskey and Savage asked this question and the problem still remains open. A solution is known only in some special cases, including perfect matchings or matchings of linear size. This article shows that the answer to the Ruskey–Savage problem is affirmative for every matching of size at most . The proof is based on an inductive construction that extends balanced matchings in the completion of the hypercube by edges of into a Hamilton cycle of . On the other hand, we show that for every there is a balanced matching in of size that cannot be extended in this way. 相似文献
105.
Monika Kořenková Dr. Ing. Martin Hejda Prof. Milan Erben Dr. Ing. Robert Jirásko Prof. Dr. Roman Jambor Prof. Aleš Růžička Dr. Elena Rychagova Prof. Sergey Ketkov Prof. Libor Dostál 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12884-12888
The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C6H3-2,6-(CH=NtBu)2) with selected N-alkyl/aryl-maleimides RN(C(O)CH)2 (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound. 相似文献
106.
107.
Katharina Zielke Ondřej Kováč Michael Winter Dr. Jiří Pospíšil Prof. Mario Waser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8163-8168
The first highly asymmetric catalytic synthesis of densely functionalized dihydrobenzofurans is reported, which starts from ortho-hydroxy-containing para-quinone methides. The reaction relies on an unprecedented formal [4+1]-annulation of these quinone methides with allenoates in the presence of a commercially available chiral phosphine catalyst. The chiral dihydrobenzofurans were obtained as single diastereomers in yields up to 90 % and with enantiomeric ratios up to 95:5. 相似文献
108.
Dr. Jana Hudecová Dr. Josef Kapitán Prof. Martin Dračínský Pavel Michal Dr. Václav Profant Prof. Petr Bouř 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202045
The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis2 complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis2 is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems. 相似文献
109.
110.
Advanced Sensing of Antibiotics with Magnetic Gold Nanocomposite: Electrochemical Detection of Chloramphenicol
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Petr Jakubec Dr. Veronika Urbanová Dr. Zdenka Medříková Prof. Dr. Radek Zbořil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14279-14284
The sensing and accurate determination of antibiotics in various environments represents a big challenge, mainly owing to their widespread use in medicine, veterinary practice, and other fields. Therefore, a new, simple electrochemical sensor for the detection of antibiotic chloramphenicol (CAP) has been developed in this work. The amplification strategy of the sensor is based on the application of magnetite nanostructures stabilized with carboxymethyl cellulose (Fe3O4‐CMC) and decorated with nanometer‐sized Au nanoparticles (NPs) (Fe3O4‐CMC@Au). In this case, CMC serves as a stabilizing agent, preventing the aggregation of Fe3O4 NPs, and hence, enabling the kinetic barrier for electron transport to be overcome, and the Au NPs serve as an electron‐conducting tunnel for better electron transport. As a proof of concept, the developed nanosensor is used for the detection of CAP in human urine samples, giving a recovery value of around 97 %, which indicates the high accuracy of the as‐prepared nanosensor. 相似文献