全文获取类型
收费全文 | 4898篇 |
免费 | 512篇 |
国内免费 | 314篇 |
专业分类
化学 | 4561篇 |
晶体学 | 18篇 |
力学 | 14篇 |
综合类 | 12篇 |
数学 | 31篇 |
物理学 | 1088篇 |
出版年
2024年 | 10篇 |
2023年 | 97篇 |
2022年 | 69篇 |
2021年 | 120篇 |
2020年 | 205篇 |
2019年 | 145篇 |
2018年 | 119篇 |
2017年 | 99篇 |
2016年 | 201篇 |
2015年 | 179篇 |
2014年 | 195篇 |
2013年 | 323篇 |
2012年 | 300篇 |
2011年 | 315篇 |
2010年 | 219篇 |
2009年 | 285篇 |
2008年 | 275篇 |
2007年 | 301篇 |
2006年 | 327篇 |
2005年 | 266篇 |
2004年 | 221篇 |
2003年 | 234篇 |
2002年 | 131篇 |
2001年 | 109篇 |
2000年 | 97篇 |
1999年 | 101篇 |
1998年 | 110篇 |
1997年 | 98篇 |
1996年 | 80篇 |
1995年 | 64篇 |
1994年 | 58篇 |
1993年 | 61篇 |
1992年 | 38篇 |
1991年 | 50篇 |
1990年 | 39篇 |
1989年 | 35篇 |
1988年 | 21篇 |
1987年 | 20篇 |
1986年 | 11篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 9篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 13篇 |
1978年 | 6篇 |
1976年 | 7篇 |
1974年 | 6篇 |
1970年 | 4篇 |
排序方式: 共有5724条查询结果,搜索用时 15 毫秒
1.
New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
2.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(12CO)4(eq-13CO)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH≠ and ΔS≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF bond) initiated the radical polymerization of vinylidene fluoride (CH2=CF2) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation. 相似文献
3.
In this work the results of the statistical topometric analysis of fracture surfaces of soda-lime-silica glass with and without ionic exchange treatment are reported. In this case, the mechanism of substitution is K+-Na+. atomic force microscopy (AFM) was employed to record the topometric data from the fracture surface. The roughness exponent (ζ) and the correlation length (ξ) were calculated by the variable bandwidth method. The analysis for both glasses (subjected and non-subjected to ionic exchange) for ζ shows a value ∼0.8, this value agrees well with that reported in the literature for rapid crack propagation in a variety of materials. The correlation length shows different values for each condition. These results, along with those of microhardness indentations suggest that the self-affine correlation length is influenced by the complex interactions of the stress field of microcracks with that resulting from the collective behavior of the point defects introduced by the strengthening mechanism of ionic exchange. 相似文献
4.
离子交换富集-导数火焰原子吸收法测定自来水中Cu,Fe和Zn 总被引:7,自引:0,他引:7
本文研究了用 2 0 1× 7阳离子交换树脂对自来水中的微量元素进行交换富集 ,采用微量脉冲进样 导数火焰原子吸收法测定富集后溶液中的Cu ,Fe和Zn ,该方法灵敏度分别为 0 2 9,0 5 9和 0 0 6 μg·L- 1 ,精密度分别为 4 2 8% ,1 95 %和 2 2 8% ,检测限分别为 1 2 8,5 85和 0 6 8μg·L- 1 ,回收率分别为 91 13% ,10 1 34%和99 84 % ,本方法大大减少了需样量 ,简便快速 ,灵敏度高。 相似文献
5.
Hai-Ping Cao 《Journal of fluorine chemistry》2006,127(8):1079-1086
In the presence of sodium dithionite and DMSO, the intramolecular radical cyclization of 4-chloro-1,1,2,2,3,3,4,4-octafluorobutylbenzenes is achieved to give the corresponding cyclic compounds in moderate to good yields. 相似文献
6.
This paper is devoted to a detailed theoretical study of an ion pair SN2 reaction LiNCO+CH3F in the gas phase and in solution at the level of MP2(full)/6-31+G**//HF/6-31+G**. Two possible reaction mechanisms, inversion and retention, are discussed. There are eight possible reaction pathways. The inversion mechanism is more favorable no matter in the gas phase or in solution based on analyses of the transition structures. Methyl isocyanate should form preferentially in the gas phase and more stable methyl cyanate is the main product in solution. The retardation of the reaction in solvents was attributed to the difference in solvation in the separated reactants and in the transition state. 相似文献
7.
Several 2- and 4-alkylcyclohexadienones were prepared and shown to accept electrons to produce ketyl radical anions that dissociated rapidly at room temperature to release carbon-centered radicals and an aromatic phenoxide type anion. In the PET process with benzyl-substituted cyclohexadienones, initiated with triethylamine, the benzyl radicals dimerised or abstracted an H-atom from solvent. In electrochemical reductions, and in reductions with alkali metals in liquid ammonia, the benzyl radicals were further reduced to anions. 相似文献
8.
9.
P. Paasche T. Valenzuela D. Biswas C. Angelescu G. Werth 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,18(3):295-300
We have examined experimentally the motional spectrum of an electron cloud confined in a Penning trap. When the axial oscillation
is excited by a radio frequency field the resonance exhibits a double structure. Both components depend differently on the
number of trapped electrons and have different shape and width. We conclude that one of them corresponds to the excitation
of the individual electrons while the other is the center-of-mass mode of the cloud. The threshold behaviour of the center-of-mass
resonance suggests that it is a parametric instability of a Mathieu type equation of motion.
Received 11 July 2001 and Received in final form 12 November 2001 相似文献
10.
L. Torrisi A.M. Mezzasalma J. Badziak J. Wolowski G. Franco 《Applied Surface Science》2006,252(24):8533-8538
High energy laser plasma-produced Cu ions have been implanted in silicon substrates placed at different distances and angles with respect to the normal to the surface of the ablated target. The implanted samples have been produced using the iodine high power Prague Asterix Laser System (PALS) using 438 nm wavelength irradiating in vacuum a Cu target. The high laser pulse energy (up to 230 J) and the short pulse duration (400 ps) produced a non-equilibrium plasma expanding mainly along the normal to the Cu target surface. Time-of-flight (TOF) technique was employed, through an electrostatic ion energy analyzer (IEA) placed along the target normal, in order to measure the ion energy, the ion charge state, the energy distribution and the charge state distribution. Ions had a Boltzmann energy distributions with an energy increasing with the charge state. At a laser fluence of the order of 6 × 106 J/cm2, the maximum ion energy was about 600 keV and the maximum charge state was about 27+.In order to investigate the implantation processes, Cu depth profiles have been performed with Rutherford backscattering spectrometry (RBS) of 1.5 MeV helium ions, Auger electron spectroscopy (AES) with 3 keV electron beam and 1 keV Ar sputtering ions in combination with scanning electron microscopy (SEM). Surface analysis results indicate that Cu ions are implanted within the first surface layers and that the ion penetration ranges are in agreement with the ion energy measured with IEA analysis. 相似文献