全文获取类型
收费全文 | 30680篇 |
免费 | 202篇 |
国内免费 | 278篇 |
专业分类
化学 | 12021篇 |
晶体学 | 274篇 |
力学 | 1402篇 |
综合类 | 12篇 |
数学 | 9178篇 |
物理学 | 8273篇 |
出版年
2022年 | 57篇 |
2021年 | 103篇 |
2020年 | 109篇 |
2019年 | 77篇 |
2018年 | 1215篇 |
2017年 | 1480篇 |
2016年 | 777篇 |
2015年 | 630篇 |
2014年 | 537篇 |
2013年 | 760篇 |
2012年 | 3250篇 |
2011年 | 2464篇 |
2010年 | 1884篇 |
2009年 | 1606篇 |
2008年 | 667篇 |
2007年 | 702篇 |
2006年 | 673篇 |
2005年 | 4493篇 |
2004年 | 3971篇 |
2003年 | 2333篇 |
2002年 | 517篇 |
2001年 | 301篇 |
2000年 | 106篇 |
1999年 | 180篇 |
1998年 | 123篇 |
1997年 | 77篇 |
1996年 | 61篇 |
1995年 | 52篇 |
1994年 | 56篇 |
1993年 | 40篇 |
1992年 | 176篇 |
1991年 | 165篇 |
1990年 | 147篇 |
1989年 | 113篇 |
1988年 | 112篇 |
1987年 | 65篇 |
1986年 | 48篇 |
1985年 | 54篇 |
1984年 | 45篇 |
1983年 | 36篇 |
1982年 | 43篇 |
1979年 | 42篇 |
1976年 | 96篇 |
1975年 | 44篇 |
1974年 | 48篇 |
1973年 | 61篇 |
1972年 | 49篇 |
1969年 | 39篇 |
1968年 | 36篇 |
1966年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons 下载免费PDF全文
Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
3.
Julia K Pruns Jens-Peter Vietzke Manfred Strassner Claudius Rapp Ulrich Hintze Wilfried A K?nig 《Rapid communications in mass spectrometry : RCM》2002,16(3):208-211
A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards. 相似文献
4.
The versatile behavior of a trihydrazidophosphoradamantane allowing the synthesis of a variety of neutral, mono- or di-cationic water-soluble molecules of potential interest for biphasic catalysis is reported. 相似文献
5.
In this paper we construct an example of a word metric on an infinite cyclic subgroup. This example shows that subexponential
distortion does not obstruct non-trivial growth of connected radii. This answers a question of Gromov [6]. The constructed
metric has other pathological properies. Specifically, its asymptotic cone depends on the choice of ultrafilter and scaling
sequence.
The work has been partially supported by the Swiss National Science Foundation. 相似文献
6.
We build a metric space which is homeomorphic to a Cantor set but cannot be realized as the attractor of an iterated function system. We give also an example of a Cantor set K in R3 such that every homeomorphism f of R3 which preserves K coincides with the identity on K. 相似文献
7.
Milan Medved? 《Journal of Mathematical Analysis and Applications》2002,267(2):643-650
A criterion for the nonexplosion of solutions to semilinear evolution equations on Banach spaces is proved. The result is obtained by applying a modification of the Bihari type inequality to the case of a weakly singular nonlinear integral inequality. 相似文献
8.
We consider the one-dimensional steady-state semiconductor deviceequations modelling a pnpn device. There are two relevant scalingsof the equations corresponding to small and large applied voltages.In both scalings, the semiconductor equations can be consideredas singularly perturbed. It turns out that the small-voltagescaling breaks down for current values between two saturationcurrents. In that interval, the large-voltage scaling has tobe employed. For both scalings, we derive the first-order termsof an asymptotic expansion and show that the reduced problemhas a solution. An example verifies that the current-voltagecurves obtained have the expected qualitative structure. 相似文献
9.
U. Kunze 《Zeitschrift für Physik B Condensed Matter》1989,76(4):463-472
Metal/insulator/semiconductor junctions are prepared on degeneratep-type InAs substrates with hole concentrations ranging from 2.3×1017 cm–3 to 2.7×1018 cm–3. The low work function of the top metal Yb, Al, or Au and charged interface states influence a two-dimensional (2D) electron inversion layer at the InAs surface. The insulator barrier that is formed by thermal oxidation is designed sufficiently thin, so that the bias voltage applied at the metal electrode mainly drops across the depletion layer separating the electron channel from the bulk. The current-voltage (I–V) characteristics exhibit strong negative differential conductance due to interband, tunneling from the 2D subband into the 3D valence band with peak-to-valley current ratios up to 3.1, 18, and 32 at 300 K, 77 K, and 4.2 K, respectively. In agreement with a theoretical model based on coherentelastic tunneling, the form of the I–V curves resembles those of double-barrier resonant tunnel devices rather than those of 3D Esaki diodes. The series resistance is obtained from the saturation of the differential conductance dI/dV at high forward bias and from the shift of structures in d2
I/dV
2 arising from phonon assisted tunneling.Dedicated to G. Lautz on the occasion of his 65th birthday 相似文献
10.
Could simple intraannular-arm macrocyclic systems exist in enantiopure stable forms? The effective synthesis of two representative compounds of such a class, their resolution into enantiomers, and experiments justifying their stability toward racemization are presented. 相似文献