全文获取类型
收费全文 | 510篇 |
免费 | 25篇 |
国内免费 | 2篇 |
专业分类
化学 | 420篇 |
晶体学 | 5篇 |
力学 | 2篇 |
数学 | 65篇 |
物理学 | 45篇 |
出版年
2023年 | 6篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 24篇 |
2019年 | 15篇 |
2018年 | 8篇 |
2017年 | 4篇 |
2016年 | 11篇 |
2015年 | 18篇 |
2014年 | 18篇 |
2013年 | 28篇 |
2012年 | 24篇 |
2011年 | 29篇 |
2010年 | 23篇 |
2009年 | 24篇 |
2008年 | 24篇 |
2007年 | 25篇 |
2006年 | 34篇 |
2005年 | 24篇 |
2004年 | 21篇 |
2003年 | 14篇 |
2002年 | 13篇 |
2001年 | 12篇 |
2000年 | 18篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1976年 | 4篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 2篇 |
1966年 | 2篇 |
1965年 | 1篇 |
1923年 | 1篇 |
1904年 | 1篇 |
排序方式: 共有537条查询结果,搜索用时 0 毫秒
1.
2.
Poly(ethylene terephthalate) film was used as supporter for preparation of polyamide layer. The most convenient method of preparation was described. This layer can be cut into any size and its sensitivity is higher than the glass plate supported layer. Twenty aromatic nitro compounds were used to show the behavior of polyester film based polyamide layer. 相似文献
3.
Tuo Jiang Samuele Bordi Angus E. McMillan Kuang-Yen Chen Fumito Saito Paula L. Nichols Benedikt M. Wanner Jeffrey W. Bode 《Chemical science》2021,12(20):6977
The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement. 相似文献
4.
A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3delta-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results. 相似文献
5.
Understanding molecular orientation on a metal surface is key to designing molecular electronic device junctions. Though platinum device electrodes are of particular interest as a more stable alternative to the often used gold electrodes, the chemisorption of conducting molecules onto platinum surfaces has not been thoroughly studied. We present herein the first detailed study of the ability and manner in which soluble oligothiophene isocyanides, of lengths ranging from 2 to 7 nm, chemisorb onto platinum surfaces and nanoparticles. It was found that these oligothiophene isocyanides stand at a 41 degrees angle from the platinum surface normal, suggesting their applicability in molecule-bridged platinum electrode devices. 相似文献
6.
Rudzevich Y Vysotsky MO Bohmer V Brody MS Rebek Jr J Broda F Thondorf I 《Organic & biomolecular chemistry》2004,2(21):3080-3084
The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2. In CDCl3 heterodimers are only observed for the combinations of 3 with 2 or 4. These results are discussed in terms of entropic and enthalpic contributions and compared with MD-simulations in a box of chloroform solvent molecules. 相似文献
7.
Iris Reimann Steffen Mergemeier Ingo Ebner Fritz Scholz 《Fresenius' Journal of Analytical Chemistry》1995,353(2):206-210
A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results. 相似文献
8.
Jiang W Wanner J Lee RJ Bounaud PY Boger DL 《Journal of the American Chemical Society》2002,124(19):5288-5290
A convergent total synthesis of the ramoplanin A2 and ramoplanose aglycon is disclosed. Three key subunits composed of residues 3-9 (heptapeptide 15), pentadepsipeptide 26, and pentapeptide 34 (residues 10-14) were prepared, sequentially coupled, and cyclized to provide the 49-membered depsipeptide core of the aglycon. Key to the preparation of the pentadepsipeptide 26 incorporating the backbone ester was the asymmetric synthesis of an orthogonally protected L-threo-beta-hydroxyasparagine and the development of effective and near-racemization free conditions for esterification of its hindered alcohol (EDCI, DMAP, 0 degrees C). The coupling sites were chosen to maximize the convergency of the synthesis including that of the three subunits, to prevent late stage racemization of carboxylate-activated phenylglycine-derived residues, and to enlist beta-sheet preorganization of an acyclic macrocyclization substrate for 49-membered ring closure. As such, macrocyclization at the chosen Phe(9)-D-Orn(10) site may benefit from both beta-sheet preorganization as well as closure at a D-amine terminus. Deliberate late stage incorporation of the subunit bearing the labile depsipeptide ester and a final stage Asn(1) side chain introduction provides future access to analogues of the aglycons which themselves are reported to be equally potent or more potent than the natural products in antimicrobial assays. 相似文献
9.
G. Wanner 《BIT Numerical Mathematics》1980,20(3):367-374
The characterization ofA-stable methods is often considered as a very difficult task (see e.g. [1]). In recent years, simple proofs have been found for methods of orderp2m-2 (see [2], [3], [7]). In this paper, we characterize theA-acceptable approximations of orderp 2m-4 and apply the result to 12-parameter families of implicit Runge-Kutta methods. 相似文献
10.
The complexes (RN=CH-CH=NR)Co(NO)(CO) with R = isopropyl, 2,6-diisopropylphenyl, or p-tolyl are chemically and electrochemically reducible to radical anions at potentials which strongly depend on R. The DFT calculated structure for the neutral compound with R = iPr agrees with the experiment, and the computed structure of the anion radical reveals changes according to a reduction of the R-DAB ligand. EPR results confirm an (R-DAB)-based singly occupied molecular orbital in [(RNCHCHNR)Co(NO)(CO)](.-), with minor but detectable contributions from NO as supported by IR spectroelectrochemistry and as quantified by DFT spin density calculations. The calculations indicate increasingly stabilized CO, NO, and RNCHCHNR pi* acceptor orbitals, in that order. On the basis of TD-DFT (time-dependent density functional theory) calculations, the lowest-lying excited states are assigned to metal-to-(R-DAB) charge transfer transitions while bands due to the metal-to-nitrosyl charge transfer occur at higher energies but still in the visible region. Resonance Raman studies were used to probe these assignments. 相似文献