全文获取类型
收费全文 | 3634篇 |
免费 | 198篇 |
国内免费 | 17篇 |
专业分类
化学 | 2466篇 |
晶体学 | 19篇 |
力学 | 107篇 |
数学 | 592篇 |
物理学 | 665篇 |
出版年
2023年 | 38篇 |
2022年 | 34篇 |
2021年 | 64篇 |
2020年 | 79篇 |
2019年 | 91篇 |
2018年 | 44篇 |
2017年 | 47篇 |
2016年 | 140篇 |
2015年 | 138篇 |
2014年 | 152篇 |
2013年 | 211篇 |
2012年 | 265篇 |
2011年 | 298篇 |
2010年 | 147篇 |
2009年 | 134篇 |
2008年 | 224篇 |
2007年 | 168篇 |
2006年 | 162篇 |
2005年 | 146篇 |
2004年 | 137篇 |
2003年 | 105篇 |
2002年 | 95篇 |
2001年 | 75篇 |
2000年 | 60篇 |
1999年 | 55篇 |
1998年 | 38篇 |
1997年 | 47篇 |
1996年 | 66篇 |
1995年 | 53篇 |
1994年 | 52篇 |
1993年 | 49篇 |
1992年 | 33篇 |
1991年 | 23篇 |
1990年 | 28篇 |
1989年 | 23篇 |
1988年 | 21篇 |
1987年 | 21篇 |
1986年 | 18篇 |
1985年 | 30篇 |
1984年 | 19篇 |
1983年 | 15篇 |
1982年 | 20篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1978年 | 16篇 |
1977年 | 10篇 |
1976年 | 11篇 |
1973年 | 16篇 |
1972年 | 10篇 |
1971年 | 9篇 |
排序方式: 共有3849条查询结果,搜索用时 0 毫秒
91.
Stephan Ludwig Dr. Kai Helmdach Mareike Hüttenschmidt Elisabeth Oberem Dr. Jabor Rabeah Dr. Alexander Villinger Prof. Dr. Ralf Ludwig Prof. Dr. Wolfram W. Seidel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16811-16817
A pair of diastereomeric dinuclear complexes, [Tp′(CO)BrW{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)(PPh3)], in which W and Ru are bridged by a phosphinyl(thiolato)alkyne in a side-on carbon P,S-chelate coordination mode, were synthesized, separated and fully characterized. Even though the isomers are similar in their spectroscopic properties and redox potentials, the like-isomer is oxidized at W while the unlike-isomer is oxidized at Ru, which is proven by IR, NIR and EPR-spectroscopy supported by spectro-electrochemistry and computational methods. The second oxidation of the complexes was shown to take place at the metal left unaffected in the first redox step. Finally, the tipping point could be realized in the unlike isomer of the electronically tuned thiophenolate congener [Tp′(CO)(PhS)W{μ-η2-C,C′-κ2-S,P-C2(PPh2)S}Ru(η5-C5H5)-(PPh3)], in which valence trapped WIII/RuII and WII/RuIII cationic species are at equilibrium. 相似文献
92.
Tim-Oliver Kindler Christoph Alberti Elena Fedorenko Nicolo Santangelo Dr. Stephan Enthaler 《ChemistryOpen》2020,9(4):401-404
The chemical recycling of end-of-life polymers can add some value to a future circular economy. In this regard, the hydrogenative degradation of end-of-life PLA was investigated to produce 1,2-propanediol as product, which is a useful building block in polymer chemistry. In more detail, the commercially available Ru-MACHO-BH complex was applied as catalyst to degrade end-of-life PLA efficiently to 1,2-propanediol under mild conditions. After investigations of the reaction conditions a set of end-of-life PLA goods were subjected to degradation. 相似文献
93.
Baptiste Joalland Nuwandi M. Ariyasingha Sren Lehmkuhl Thomas Theis Stephan Appelt Eduard Y. Chekmenev 《Angewandte Chemie (International ed. in English)》2020,59(22):8654-8660
Radio amplification by stimulated emission of radiation (RASER) was recently discovered in a low‐field NMR spectrometer incorporating a highly specialized radio‐frequency resonator, where a high degree of proton‐spin polarization was achieved by reversible parahydrogen exchange. RASER activity, which results from the coherent coupling between the nuclear spins and the inductive detector, can overcome the limits of frequency resolution in NMR. Here we show that this phenomenon is not limited to low magnetic fields or the use of resonators with high‐quality factors. We use a commercial bench‐top 1.4 T NMR spectrometer in conjunction with pairwise parahydrogen addition producing proton‐hyperpolarized molecules in the Earth's magnetic field (ALTADENA condition) or in a high magnetic field (PASADENA condition) to induce RASER without any radio‐frequency excitation pulses. The results demonstrate that RASER activity can be observed on virtually any NMR spectrometer and measures most of the important NMR parameters with high precision. 相似文献
94.
Prof. Dr. Igor Savić Prof. Dr. Stephan Schlemmer Prof. Dr. Dieter Gerlich 《Chemphyschem》2020,21(13):1429-1435
In order to study collisions between ions and neutrals, a new Guided Ion Beam (GIB) apparatus, called NOVion, has been assembled and tested. The primary purpose of this instrument is to measure absolute cross sections at energies relevant for technical or inter- and circumstellar plasmas. New and improved results are presented for forming H3+ in collisions of H2+ with H2. Between 0.1 eV and 2 eV, our measured effective cross sections are in good overall agreement with most previous measurements. However, at higher energies, our results do not show the steep decline, recommended in the standard literature. After critical evaluation of all experimental and theoretical data, a new analytical function is proposed, describing properly the dependence of the title reaction on the collision energy up to 10 eV. 相似文献
95.
The development of a novel generation of excimer UV lamps enables versatile applications of quasi-monochromatic UV radiation. For example, xenon-excimer flow-through photoreactors may be used for wastewater treatment. The vacuum-UV radiation (λ = 172 nm) initiates water cleavage with formation of H atoms and oxidizing hydroxyl radicals. The latter are responsible for the photomineralization of organic substrates. An automated model reactor demonstrates the basic concepts of this advanced oxidation process. 相似文献
96.
97.
98.
Jérôme Deprince Manuel Bautista Stephan Fritzsche Javier García Timothy Kallman Claudio Mendoza Patrick Palmeri Pascal Quinet 《X射线光谱测定》2020,49(1):29-32
In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 105 to 107 K and an electron density ranging from 1018 to 1022 cm−3. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions. 相似文献
99.
Quantification of veterinary antibiotics (sulfonamides and trimethoprim) in animal manure by liquid chromatography-mass spectrometry 总被引:22,自引:0,他引:22
Haller MY Müller SR McArdell CS Alder AC Suter MJ 《Journal of chromatography. A》2002,952(1-2):111-120
A fast and cost effective method was developed to extract and quantify residues of veterinary antimicrobial agents (antibiotics) in animal manure by liquid-liquid extraction and liquid chromatography-mass spectrometry. The compounds investigated include six sulfonamides, one metabolite, and trimethoprim. The method was performed without sample clean up. Recoveries from spiked manure slurry samples (spike level = 1 mg/kg) were as follows: sulfaguanidine (52%), sulfadiazine (47%), sulfathiazole (64%), sulfamethazine (89%), its metabolite N4-acetyl-sulfamethazine (88%), sulfamethoxazole (84%), sulfadimethoxine (51%), and trimethoprim (64%). Relative standard deviations of the recoveries were less than 5% within the same day and less than 20% between days. The limit of quantification was below 0.1 mg/kg liquid manure slurry for all compounds and calibration curves obtained from extracts of spiked samples were linear up to a level of 5 mg/kg liquid manure, except for trimethoprim (0.01-0.5 mg/kg). Analysis of six grab samples taken in Switzerland from manure pits on farms where medicinal feed had been applied revealed total sulfonamide concentrations of up to 20 mg/kg liquid manure. 相似文献
100.
Stephan Schaumüller Doris Cristurean Stephan Haudum George S. Pappas Markus Himmelsbach Matthias Bechmann Oliver Brüggemann Ian Teasdale 《Journal of polymer science. Part A, Polymer chemistry》2021,59(24):3161-3166
We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials. 相似文献