全文获取类型
收费全文 | 6822篇 |
免费 | 178篇 |
国内免费 | 18篇 |
专业分类
化学 | 4397篇 |
晶体学 | 46篇 |
力学 | 143篇 |
数学 | 1044篇 |
物理学 | 1388篇 |
出版年
2021年 | 51篇 |
2020年 | 66篇 |
2019年 | 77篇 |
2018年 | 65篇 |
2017年 | 49篇 |
2016年 | 116篇 |
2015年 | 112篇 |
2014年 | 127篇 |
2013年 | 308篇 |
2012年 | 236篇 |
2011年 | 273篇 |
2010年 | 222篇 |
2009年 | 181篇 |
2008年 | 263篇 |
2007年 | 253篇 |
2006年 | 239篇 |
2005年 | 248篇 |
2004年 | 236篇 |
2003年 | 227篇 |
2002年 | 237篇 |
2001年 | 120篇 |
2000年 | 143篇 |
1999年 | 114篇 |
1998年 | 81篇 |
1997年 | 91篇 |
1996年 | 109篇 |
1995年 | 82篇 |
1994年 | 114篇 |
1993年 | 110篇 |
1992年 | 90篇 |
1991年 | 97篇 |
1990年 | 79篇 |
1989年 | 73篇 |
1988年 | 63篇 |
1987年 | 67篇 |
1986年 | 80篇 |
1985年 | 132篇 |
1984年 | 91篇 |
1983年 | 82篇 |
1982年 | 108篇 |
1981年 | 106篇 |
1980年 | 140篇 |
1979年 | 101篇 |
1978年 | 114篇 |
1977年 | 130篇 |
1976年 | 106篇 |
1975年 | 101篇 |
1974年 | 80篇 |
1973年 | 86篇 |
1972年 | 56篇 |
排序方式: 共有7018条查询结果,搜索用时 78 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.
Acta Mathematica Hungarica - Minkowski’s classical existence theorem provides necessary and sufficient conditions for a Borel measure on the unit sphere of Euclidean space to be the surface... 相似文献
3.
Dr. Sabin Llona‐Minguez Dr. Matthieu Desroses Artin Ghassemian Dr. Sylvain A. Jacques Dr. Lars Eriksson Rebecka Isacksson Tobias Koolmeister Dr. Pål Stenmark Dr. Martin Scobie Prof. Thomas Helleday 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7394-7398
A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif. 相似文献
4.
Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Bernadette Graff Didier Gigmes Jean Pierre Fouassier Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(5):665-674
Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674 相似文献
5.
Dr. Felipe L. Coelho Eduarda S. Gil Dr. Paulo F. B. Gonçalves Dr. Leandra F. Campo Dr. Paulo H. Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8157-8162
In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles. 相似文献
6.
7.
This paper describes several combinatorial models for Laguerre, Charlier, and Hermite polynomials, and uses them to prove combinatorially some classical formulas. The so-called “Italian limit formula” (from Laguerre to Hermite), the Appel identity for Hermite polynomials, and the two Sheffer identities for Laguerre and Charlier polynomials are proved. We also give bijective proofs of the three-term recurrences. These three families form the bottom triangle in R. Askey's chart classifying hypergeometric orthogonal polynomials. 相似文献
8.
We consider front solutions of the Swift–Hohenberg equation ∂
t
u= -(1+ ∂
x
2)2
u + ɛ2
u -u
3. These are traveling waves which leave in their wake a periodic pattern in the laboratory frame. Using renormalization techniques
and a decomposition into Bloch waves, we show the non-linear stability of these solutions. It turns out that this problem
is closely related to the question of stability of the trivial solution for the model problem ∂
t
u(x,t) = ∂
x
2
u (x,t)+(1+tanh(x-ct))u(x,t)+u(x,t)
p
with p>3. In particular, we show that the instability of the perturbation ahead of the front is entirely compensated by a diffusive
stabilization which sets in once the perturbation has hit the bulk behind the front.
Received: 23 February 2001 / Accepted: 27 August 2001 相似文献
9.
Guido Wauters Jacques Dewaele Carlo Vandecasteele Richard Dams 《Mikrochimica acta》1989,98(4-6):157-162
Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the111,112Cd(p, xn)111 In and the206,207,208Pb(p, xn)206Bi reactions.111In and206Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values. 相似文献
10.