全文获取类型
收费全文 | 1186篇 |
免费 | 56篇 |
国内免费 | 8篇 |
专业分类
化学 | 759篇 |
晶体学 | 9篇 |
力学 | 46篇 |
数学 | 250篇 |
物理学 | 186篇 |
出版年
2023年 | 14篇 |
2022年 | 25篇 |
2021年 | 23篇 |
2020年 | 34篇 |
2019年 | 25篇 |
2018年 | 27篇 |
2017年 | 19篇 |
2016年 | 70篇 |
2015年 | 28篇 |
2014年 | 39篇 |
2013年 | 89篇 |
2012年 | 102篇 |
2011年 | 98篇 |
2010年 | 60篇 |
2009年 | 37篇 |
2008年 | 71篇 |
2007年 | 71篇 |
2006年 | 56篇 |
2005年 | 68篇 |
2004年 | 22篇 |
2003年 | 31篇 |
2002年 | 29篇 |
2001年 | 17篇 |
2000年 | 19篇 |
1999年 | 17篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 12篇 |
1995年 | 6篇 |
1993年 | 6篇 |
1992年 | 9篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 12篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1974年 | 10篇 |
1972年 | 4篇 |
1970年 | 2篇 |
1966年 | 4篇 |
排序方式: 共有1250条查询结果,搜索用时 15 毫秒
71.
Antoine Versini Lou Saier Fabien Sindikubwabo Sebastian Müller Tatiana Cañeque Raphaël Rodriguez 《Tetrahedron》2018,74(39):5585-5614
Cancer stem cells (CSC) have been shown to be refractory to conventional therapeutic agents, can promote metastasis, and have been linked to cancer relapse. The natural product Salinomycin has been identified by means of high throughput phenotypic screening as a selective killer of CSC in vitro and in vivo. In this article we comprehensively review the chemistry of Salinomycin, documenting early total syntheses, along with strategies that have been developed over the years to effectively modify this natural product at key positions with the view to establish a robust structure-activity-relationship and to delineate the complex mechanism of action of this fascinating molecule in the context of cancer research. Then, we document the biology of Salinomycin, putting forward phenotypic alterations that have been observed in the relevant biological models and highlighting how chemistry has been instrumental in discovering unprecedented physiological features of cancer stem cells that can be exploited for therapeutic benefits. 相似文献
72.
Dr. Ricardo Rodriguez Dr. Yohan Contie Raphael Nougué Dr. Antoine Baceiredo Dr. Nathalie Saffon‐Merceron Dr. Jean‐Marc Sotiropoulos Dr. Tsuyoshi Kato 《Angewandte Chemie (International ed. in English)》2016,55(46):14355-14358
Phosphine‐stabilized silylenes react with silanes and a phosphine by silylene insertion into E?H σ‐bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step. 相似文献
73.
Weronika Gruszka Anna Lykkeberg Gary S. Nichol Michael P. Shaver Antoine Buchard Jennifer A. Garden 《Chemical science》2020,11(43):11785
Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver “best of both” in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (kobs = 1.7 × 10−2 s−1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.Cooperative heterotrimetallic Na/Zn2 and K/Zn2 complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation. 相似文献
74.
Antoine Tiya Djowe Samuel Laminsi Daniel Njopwouo Elie Acayanka Eric M. Gaigneaux 《Plasma Chemistry and Plasma Processing》2013,33(4):707-723
Smectite clay from Sabga (west-Cameroon) was treated in aqueous suspension by gliding arc plasma to modify its surface properties. The evolution of the modifications was followed with the exposure time and post-discharge duration using Fourier transformed infra red spectroscopy and scanning electron microscopy. X-ray diffraction and nitrogen physisorption analyses were also performed to evaluate if both crystalline and textural properties of the material are affected by the treatment. The results obtained show that the plasma treatment causes the breakdown of structural bounds at the clay surface and induces the formation of new hydroxyl groups (Si–OH and Al–OH) on the clay edges. Crystallinity, sheet structure and textural properties are not significantly affected by the plasma treatment. However, it should be noted that an intensive treatment of the clay lowers the pH of the suspension, which subsequently induces an acid attack of the clay. In such case, the specific surface area of the clay increases. This study demonstrates that gliding arc plasma treatments can be used to activate clay minerals for environmental application. 相似文献
75.
Kadish KM Wang LL Thuriere A Giribabu L Garcia R Van Caemelbecke E Bear JL 《Inorganic chemistry》2003,42(25):8309-8319
Three Ru2(5+) diruthenium complexes, (4,0) Ru2(2-CH3ap)4Cl, (3,1) Ru2(2-Fap)4Cl, and (3,1) Ru2(2,4,6-F3ap)4Cl where ap is the 2-anilinopyridinate anion, were examined as to their electrochemical and spectroelectrochemical properties in five different nonaqueous solvents (CH2Cl2, THF, PhCN, DMF, and DMSO). Each compound undergoes a single one-electron metal-centered oxidation in THF, DMF, and DMSO and two one-electron metal-centered oxidations in CH2Cl2 and PhCN. The three diruthenium complexes also undergo two reductions in each solvent except for CH2Cl2, and these electrode processes are assigned as Ru2(5+/4+) and Ru2(4+/3+). Each neutral, singly reduced, and singly oxidized species was characterized by UV-vis thin-layer spectroelectrochemistry, and the data are discussed in terms of the most probable electronic configuration of the compound in solution. The three neutral complexes contain three unpaired electrons as indicated by magnetic susceptibility measurements using the Evans method (3.91-3.95 muB), and the electronic configuration is assigned as sigma2pi4delta2pi(*2)delta, independent of the solvent. The three singly oxidized compounds have two unpaired electrons in CD2Cl2, DMSO-d6, or CD3CN (2.65-3.03 muB), and the electronic configuration is here assigned as sigma2pi4delta2pi(*2). The singly reduced compound also has two unpaired electrons (2.70-2.80 muB) in all three solvents, consistent with the electronic configuration sigma2pi4delta2pi(*2)delta(*2) or sigma2pi4delta2pi(*3)delta*. Finally, the overall effect of solvent on the number of observed redox processes is discussed in terms of solvent binding, and several formation constants were calculated. 相似文献
76.
77.
Sakey Ravindra Kokkarachedu Varaprasad V. Rajinikanth Antoine F. Mulaba-Bafubiandi Koduri Venkata Surya Ramam 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1230-1240
Design of silver nanoparticles containing poly(N-isopropylarclamide) (PNIPAAm) hydrogels were prepared by free-radical polymerization of N-isopropylarclamide as an environmentally sensitive monomer and MBA as a crosslinker in an aqueous medium. The embedded silver nanocomposite hydrogels (AgNCH) structure were characterized by, UV-Vis, FTIR, DLS, TEM and X-ray analysis. Curcumin loading and release characteristics were performed for PNIPAAm hydrogel, silver ions loaded hydrogels as well as silver nanocomposite hydrogels. These curcumin loaded silver nanocomposite hydrogels exhibit excellent antibacterial action on Escherichia coli (E. coli). Therefore, the present study clearly provides novel antimicrobial hydrogels which are potentially useful in biomedical applications. 相似文献
78.
Dr. Pierre‐Antoine Bouit Magdalena Marszalek Dr. Robin Humphry‐Baker Dr. Rafael Viruela Prof. Dr. Enrique Ortí Dr. Shaik M. Zakeeruddin Prof. Dr. Michael Grätzel Dr. Juan Luis Delgado Prof. Dr. Nazario Martín 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(37):11621-11629
Two donor–acceptor molecular tweezers incorporating the 10‐(1,3‐dithiol‐2‐ylidene)anthracene unit as donor group and two cyanoacrylic units as accepting/anchoring groups are reported as metal‐free sensitizers for dye‐sensitized solar cells. By changing the phenyl spacer with 3,4‐ethylenedioxythiophene (EDOT) units, the absorption spectrum of the sensitizer is red‐shifted with a corresponding increase in the molar absorptivity. Density functional calculations confirmed the intramolecular charge‐transfer nature of the lowest‐energy absorption bands. The new dyes are highly distorted from planarity and are bound to the TiO2 surface through the two anchoring groups in a unidentate binding form. A power‐conversion efficiency of 3.7 % was obtained with a volatile CH3CN‐based electrolyte, under air mass 1.5 global sunlight. Photovoltage decay transients and ATR‐FTIR measurements allowed us to understand the photovoltaic performance, as well as the surface binding, of these new sensitizers. 相似文献
79.
Anne-Marie Caminade Fayez El Khatib Antoine Baceiredo Max Koenig 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2-4):365-367
Abstract The ozonization of various halophosphines 1a-j leads with quantitative yields to the corresponding phosphine oxides 2a-j. Ozonization is a convenient method of oxidation, in particular of compounds with bulky ligands (1c, 1d, 1e). 相似文献
80.
Dr. Justine Harmel Dr. Laurent Peres Dr. Marta Estrader Adrien Berliet Dr. Sylvie Maury Dr. Antoine Fécant Dr. Bruno Chaudret Prof. Dr. Philippe Serp Dr. Katerina Soulantica 《Angewandte Chemie (International ed. in English)》2018,57(33):10579-10583
The Fischer–Tropsch synthesis (FTS) is a structure‐sensitive exothermic reaction that enables catalytic transformation of syngas to high quality liquid fuels. Now, monolithic cobalt‐based heterogeneous catalysts were elaborated through a wet chemistry approach that allows control over nanocrystal shape and crystallographic phase, while at the same time enables heat management. Copper and nickel foams have been employed as supports for the epitaxial growth of hcp‐Co nanowires directly from a solution containing a coordination compound of cobalt and stabilizing ligands. The Co/Cufoam catalyst was tested for Fischer–Tropsch synthesis in a fixed‐bed reactor, showing stability and significantly superior activity and selectivity towards C5+ compared to a Co/SiO2‐Al2O3 reference catalyst under the same conditions. 相似文献