全文获取类型
收费全文 | 3200篇 |
免费 | 662篇 |
国内免费 | 214篇 |
专业分类
化学 | 2828篇 |
晶体学 | 21篇 |
力学 | 101篇 |
综合类 | 26篇 |
数学 | 820篇 |
物理学 | 280篇 |
出版年
2024年 | 1篇 |
2023年 | 34篇 |
2022年 | 33篇 |
2021年 | 54篇 |
2020年 | 151篇 |
2019年 | 111篇 |
2018年 | 96篇 |
2017年 | 71篇 |
2016年 | 200篇 |
2015年 | 202篇 |
2014年 | 203篇 |
2013年 | 303篇 |
2012年 | 246篇 |
2011年 | 276篇 |
2010年 | 218篇 |
2009年 | 254篇 |
2008年 | 249篇 |
2007年 | 193篇 |
2006年 | 197篇 |
2005年 | 166篇 |
2004年 | 162篇 |
2003年 | 163篇 |
2002年 | 84篇 |
2001年 | 41篇 |
2000年 | 47篇 |
1999年 | 52篇 |
1998年 | 40篇 |
1997年 | 73篇 |
1996年 | 26篇 |
1995年 | 19篇 |
1994年 | 19篇 |
1993年 | 15篇 |
1992年 | 15篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1969年 | 1篇 |
排序方式: 共有4076条查询结果,搜索用时 234 毫秒
21.
The homogeneous and heterogeneous reactions in the boundary-layer of a flat surface are considered. The autocatalysts are assumed to be of regular sizes, while the solution is a dilute nanofluid. The heat release due to the chemical reactions is taken into account. The Buongiorno's model is used to describe the behaviors of this reaction system. This configuration makes the current model be different from all previous publications. Multiple solutions are given numerically to the rescaled nonlinear system, whose stability is verified. The results show that the strength coefficients of the homogeneous and heterogeneous reactions are key factors to cause the appearance of the multiple solutions in the distribution of the chemical reactions. Nanofluids enhance the diffusion of heat and help maintain the stability of chemical reactions. 相似文献
22.
Murugan Subaramanian Vinod G. Landge Akash Mondal Virendrakumar Gupta Ekambaram Balaraman 《化学:亚洲杂志》2019,14(24):4557-4562
A molecularly defined NiII‐complex catalyzing the chemoselective acetalization of aldehydes with alcohols under neutral conditions is reported. The reaction is general, efficient and showed a wide substrate scope (including aliphatic aldehydes) as well as excellent functional group tolerance. Reusability of the present nickel catalyst is also demonstrated. 相似文献
23.
24.
Dr. Massimo Rigo Evi R. M. Habraken Dr. Koyel Bhattacharyya Manuela Weber Dr. Andreas W. Ehlers Dr. Nicolas Mézailles Dr. J. Chris Slootweg Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8769-8779
A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur) was calculated to get insight into the steric properties, [LNi(CO)3] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts. 相似文献
25.
Dr. Yohei Ogiwara Yurika Iino Prof. Dr. Norio Sakai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6513-6516
A method for the palladium/copper-catalyzed direct acylation of azoles with acyl fluorides is described. This study reports the first examples of acyl fluorides being used as acylation reagents in transition-metal-catalyzed aromatic C−H bond functionalization reactions. Depending on the reaction temperature, decarbonylative coupling may also occur. Mechanistic studies suggest that the cleavage of the aromatic C−H bond, promoted by a copper-phosphine species, is not the rate-limiting step of this acylation. 相似文献
26.
Giovanni Calvaruso Reinier Storm Joeri Van der Veken 《Mathematische Nachrichten》2020,293(9):1707-1729
We classify totally geodesic and parallel hypersurfaces of four-dimensional non-reductive homogeneous pseudo-Riemannian manifolds. 相似文献
27.
Nikolay K. Vitanov Zlatinka I. Dimitrova Kaloyan N. Vitanov 《Entropy (Basel, Switzerland)》2021,23(1)
The goal of this article is to discuss the Simple Equations Method (SEsM) for obtaining exact solutions of nonlinear partial differential equations and to show that several well-known methods for obtaining exact solutions of such equations are connected to SEsM. In more detail, we show that the Hirota method is connected to a particular case of SEsM for a specific form of the function from Step 2 of SEsM and for simple equations of the kinds of differential equations for exponential functions. We illustrate this particular case of SEsM by obtaining the three- soliton solution of the Korteweg-de Vries equation, two-soliton solution of the nonlinear Schrödinger equation, and the soliton solution of the Ishimori equation for the spin dynamics of ferromagnetic materials. Then we show that a particular case of SEsM can be used in order to reproduce the methodology of the inverse scattering transform method for the case of the Burgers equation and Korteweg-de Vries equation. This particular case is connected to use of a specific case of Step 2 of SEsM. This step is connected to: (i) representation of the solution of the solved nonlinear partial differential equation as expansion as power series containing powers of a “small” parameter ; (ii) solving the differential equations arising from this representation by means of Fourier series, and (iii) transition from the obtained solution for small values of to solution for arbitrary finite values of . Finally, we show that the much-used homogeneous balance method, extended homogeneous balance method, auxiliary equation method, Jacobi elliptic function expansion method, F-expansion method, modified simple equation method, trial function method and first integral method are connected to particular cases of SEsM. 相似文献
28.
《Mendeleev Communications》2022,32(5):576-578
Novel highly soluble palladium-based complexes with ferrocenecarboxylic acid of general formula [Pd(lut)2(FcCOO)2] (lut is 2,6-or 3,4-lutidines) were synthesized and structurally characterized by single-crystal X-ray diffraction. The catalytic oxidation of 1,2-diphenyl-acetylene with these complexes gave dibenzo[a,e]pentalene derivative along with other products. 相似文献
29.
Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism 下载免费PDF全文
Prof. Bert U. W. Maes Dr. Stefan Verbeeck Dr. Tom Verhelst Audrey Ekomié Niklas von Wolff Dr. Guillaume Lefèvre Dr. Emily A. Mitchell Prof. Anny Jutand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7858-7865
The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd0(PPh3)2] (generated from [Pd0(PPh3)4]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented SNAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies. 相似文献
30.
Neal P. Mankad 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5822-5829
An emerging area of homogeneous catalysis is the use of catalysts featuring two closely associated metal sites. This approach complements the traditional focus on single‐site catalysts and makes available new parameters with which to optimize catalytic behavior. Single‐site catalysts are optimized through changing 1) the identity of the metal, and 2) the steric and electronic properties of the ligands. Bimetallic catalysts introduce new optimization parameters such as 3) catalyst nuclearity (mononuclear vs. binuclear), and 4) bimetallic pairing (relative compatibility of two metal sites). In order to harness these new optimization parameters in developing systems, it is necessary to first understand the origin of bimetallic selectivity effects that already have been documented. This Concept article highlights bimetallic effects on the chemo‐, regio‐, and stereoselectivity of catalytic transformations, using selected case studies from the recent literature as illustrative examples. 相似文献