全文获取类型
收费全文 | 36979篇 |
免费 | 4630篇 |
国内免费 | 3982篇 |
专业分类
化学 | 13949篇 |
晶体学 | 86篇 |
力学 | 2892篇 |
综合类 | 302篇 |
数学 | 20292篇 |
物理学 | 8070篇 |
出版年
2024年 | 101篇 |
2023年 | 450篇 |
2022年 | 637篇 |
2021年 | 872篇 |
2020年 | 1242篇 |
2019年 | 1283篇 |
2018年 | 1090篇 |
2017年 | 1185篇 |
2016年 | 1576篇 |
2015年 | 1421篇 |
2014年 | 1985篇 |
2013年 | 3750篇 |
2012年 | 2078篇 |
2011年 | 2390篇 |
2010年 | 2009篇 |
2009年 | 2575篇 |
2008年 | 2506篇 |
2007年 | 2583篇 |
2006年 | 2265篇 |
2005年 | 1789篇 |
2004年 | 1567篇 |
2003年 | 1480篇 |
2002年 | 1255篇 |
2001年 | 1009篇 |
2000年 | 1021篇 |
1999年 | 878篇 |
1998年 | 730篇 |
1997年 | 699篇 |
1996年 | 483篇 |
1995年 | 354篇 |
1994年 | 315篇 |
1993年 | 228篇 |
1992年 | 227篇 |
1991年 | 159篇 |
1990年 | 146篇 |
1989年 | 114篇 |
1988年 | 94篇 |
1987年 | 78篇 |
1986年 | 71篇 |
1985年 | 106篇 |
1984年 | 134篇 |
1983年 | 68篇 |
1982年 | 101篇 |
1981年 | 96篇 |
1980年 | 89篇 |
1979年 | 76篇 |
1978年 | 72篇 |
1977年 | 49篇 |
1976年 | 44篇 |
1975年 | 13篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
2.
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
3.
《Indagationes Mathematicae》2021,32(1):55-85
We show that the differential structure of the orbit space of a proper action of a Lie group on a smooth manifold is weakly reflexive. This implies that the orbit space is a differentiable space in the sense of Smith, which ensures that the orbit space has an exterior algebra of differential forms, that satisfies Smith’s version of de Rham’s theorem. Because the orbit space is a locally closed subcartesian space, it has vector fields and their flows. 相似文献
4.
M. Amar D. Andreucci R. Gianni C. Timofte 《Journal of Mathematical Analysis and Applications》2021,493(2):124533
We prove a well-posedness result for two pseudo-parabolic problems, which can be seen as two models for the same electrical conduction phenomenon in heterogeneous media, neglecting the magnetic field. One of the problems is the concentration limit of the other one, when the thickness of the dielectric inclusions goes to zero. The concentrated problem involves a transmission condition through interfaces, which is mediated by a suitable Laplace-Beltrami type equation. 相似文献
5.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
6.
Bifurcation analysis of visual angle model with anticipated time and stabilizing driving behavior
下载免费PDF全文
![点击此处可从《中国物理 B》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Xueyi Guan 《中国物理 B》2022,31(7):70507-070507
In the light of the visual angle model (VAM), an improved car-following model considering driver's visual angle, anticipated time and stabilizing driving behavior is proposed so as to investigate how the driver's behavior factors affect the stability of the traffic flow. Based on the model, linear stability analysis is performed together with bifurcation analysis, whose corresponding stability condition is highly fit to the results of the linear analysis. Furthermore, the time-dependent Ginzburg-Landau (TDGL) equation and the modified Korteweg-de Vries (mKdV) equation are derived by nonlinear analysis, and we obtain the relationship of the two equations through the comparison. Finally, parameter calibration and numerical simulation are conducted to verify the validity of the theoretical analysis, whose results are highly consistent with the theoretical analysis. 相似文献
7.
8.
9.
10.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献