全文获取类型
收费全文 | 1418篇 |
免费 | 35篇 |
国内免费 | 7篇 |
专业分类
化学 | 985篇 |
晶体学 | 4篇 |
力学 | 60篇 |
数学 | 235篇 |
物理学 | 176篇 |
出版年
2023年 | 7篇 |
2022年 | 6篇 |
2021年 | 37篇 |
2020年 | 30篇 |
2019年 | 27篇 |
2018年 | 23篇 |
2017年 | 24篇 |
2016年 | 44篇 |
2015年 | 21篇 |
2014年 | 41篇 |
2013年 | 69篇 |
2012年 | 68篇 |
2011年 | 89篇 |
2010年 | 52篇 |
2009年 | 58篇 |
2008年 | 82篇 |
2007年 | 106篇 |
2006年 | 97篇 |
2005年 | 76篇 |
2004年 | 86篇 |
2003年 | 49篇 |
2002年 | 42篇 |
2001年 | 11篇 |
2000年 | 15篇 |
1998年 | 11篇 |
1997年 | 7篇 |
1996年 | 13篇 |
1995年 | 18篇 |
1994年 | 8篇 |
1993年 | 11篇 |
1992年 | 10篇 |
1991年 | 17篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1988年 | 17篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 11篇 |
1984年 | 13篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 16篇 |
1980年 | 13篇 |
1979年 | 17篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1976年 | 13篇 |
1975年 | 6篇 |
1974年 | 8篇 |
1973年 | 4篇 |
排序方式: 共有1460条查询结果,搜索用时 125 毫秒
1.
2.
Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair
Dr. María Carmona Dr. Joaquina Ferrer Dr. Ricardo Rodríguez Dr. Vincenzo Passarelli Prof. Dr. Fernando J. Lahoz Dr. Pilar García-Orduña Dr. Laura Cañadillas-Delgado Prof. Dr. Daniel Carmona 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13665-13670
[Cp*Rh(κ3N,N′,P- L )][SbF6] (Cp*=C5Me5), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H2 and H2O in a reversible manner. When D2O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp3)−H bond activation. 相似文献
3.
4.
Victor B. Tinti Debora Marani Andre S. Ferlauto Fabio C. Fonseca Vincenzo Esposito Daniel Z. de Florio 《Particle & Particle Systems Characterization》2020,37(2):1900472
A fast and accurate experimental method is demonstrated to assess the fraction of exsolved metallic nanoparticles using magnetic measurements. As a benchmark, nanometric metallic nickel exsolved from (La1−xSrx)(Cr1−yNiy)O3−δ is used for its high relevance as a solid oxide fuel cell component. The method is based on the difference in the magnetic response of the exsolved metallic nickel (ferromagnetic) and Sr-doped lanthanum chromite ceramic matrix (paramagnetic). The exsolved nickel results in coherent nanoparticles pinned on the surface of the Sr-doped lanthanum chromite ceramic matrix, as evidenced by electron microscopy analyses. The results obtained indicate the procedure as a fast and sensitive method to study the exsolution of ferromagnetic nanoparticles. 相似文献
5.
Georgia Englezou Kristoffer Kortsen Ana A. C. Pacheco Robert Cavanagh Joachim C. Lentz Eduards Krumins Carlos Sanders-Velez Steven M. Howdle Alisyn J. Nedoma Vincenzo Taresco 《Journal of polymer science. Part A, Polymer chemistry》2020,58(11):1571-1581
2-methyltetrahydrofuran (2-MeTHF) is a readily available, inexpensive, neoteric, bio-based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring opening polymerizations. To reduce the environmental burden related to the synthesis of pharmaceutical-grade polymers based on lactide and caprolactone, we envisaged the use of 2-MeTHF. For the first time, we combined a series of metal-free and enzymatic ROPs with free radical and controlled RAFT polymerizations (carried out separately and in tandem) in 2-MeTHF, in order to easily tune the chemistry and the architecture of the final polymers. After a simple purification, the amphiphilic polymers were formulated into nanoparticles and tested for their cytocompatibility in three model cell lines, to assess their application as potential polymeric excipients for nanomedicines. 相似文献
6.
Alessio Melli Simone Potenti Dr. Mattia Melosso Dr. Sven Herbers Dr. Lorenzo Spada Dr. Andrea Gualandi Kevin G. Lengsfeld Prof. Luca Dore Philipp Buschmann Prof. Pier Giorgio Cozzi Prof. Jens-Uwe Grabow Prof. Vincenzo Barone Prof. Cristina Puzzarini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):15016-15022
Phenylmethanimine is an aromatic imine with a twofold relevance in chemistry: organic synthesis and astrochemistry. To tackle both aspects, a multidisciplinary strategy has been exploited and a new, easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, based on the thermal decomposition of hydrobenzamide, with a state-of-the-art computational characterization of phenylmethanimine laid the foundation for its first laboratory observation by means of rotational electric resonance spectroscopy. Both E and Z isomers have been accurately characterized, thus providing a reliable basis to guide future astronomical observations. A further characterization has been carried out by nuclear magnetic resonance spectroscopy, showing the feasibility of this synthetic approach in solution. The temperature dependence as well as possible mechanisms of the thermolysis process have been examined. 相似文献
7.
Vincenzo Palleschi 《Frontiers of Physics》2021,16(2):22503
A recent paper [1 ] by the group of Prof. Zhe Wang, Beijing, China reveals the physical mechanism responsible of the signal fluctuations in laser-induced breakdown spectroscopy analysis. 相似文献
8.
2 a and 2 b , [Ir(CI)(COD)(NHC)] (COD=1,5-cyclooctadiene), have been prepared via transmetallation from NHC−Ag complexes. [Rh(CI)(COD)(NHC)] ( 4 ) was prepared analogously. [Ir({κ-C,N-(NHC-acetamide−1H)}(COD)] ( 3 c ) has been synthesized via transmetallation from the deprotonated NHC−Ag complex. [IrCp*({κ-C,N-(NHC-acetamide−1H)}] ( 5 ) (Cp*=pentamethylcyclopentadienyl), has been obtained analogously. [Ir(CI)(CO)2(NHC)] ( 6 ) and [Ir({κ-C,N-(NHC-acetamide−1H)}(CO)2] ( 7 ) have been prepared by carbonylation of 2 b and 3 c , respectively. The catalytic activity of these complexes has been evaluated in the dehydrogenation of formic acid, under solventless conditions, in the presence of water as a cosolvent, and in a 5 : 2 HCOOH/Et3N mixture, with the best TOF values being obtained in the case of the latter. Stoichiometric experiments suggest COD hydrogenation as the preactivation step. 相似文献
9.
Probing the Coordinative Unsaturation and Local Environment of Ti3+ Sites in an Activated High‐Yield Ziegler–Natta Catalyst 下载免费PDF全文
Elena Morra Prof. Elio Giamello Prof. Sabine Van Doorslaer Giuseppe Antinucci Dr. Maddalena D'Amore Prof. Vincenzo Busico Prof. Mario Chiesa 《Angewandte Chemie (International ed. in English)》2015,54(16):4857-4860
The typical activation of a fourth generation Ziegler–Natta catalyst TiCl4/MgCl2/phthalate with triethyl aluminum generates Ti3+ centers that are investigated by multi‐frequency continuous wave and pulse EPR methods. Two families of isolated, molecule‐like Ti3+ species have been identified. A comparison of the experimentally derived g tensors and 35,37Cl hyperfine and nuclear‐quadrupole tensors with DFT‐computed values suggests that the dominant EPR‐active Ti3+ species is located on MgCl2(110) surfaces (or equivalent MgCl2 terminations with tetra‐coordinated Mg). O2 reactivity tests show that a fraction of these Ti sites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization. 相似文献
10.
Pietro?CalandraEmail author Tilde?de?Caro Daniela?Caschera Domenico?Lombardo Lorena?Todaro Vincenzo?Turco Liveri 《Colloid and polymer science》2015,293(2):597-603
The spectroscopic properties and liquid structure of pure tri-n-butyl phosphate (TBP) and FeCl3/TBP solutions have been investigated by Uv–Vis and Raman spectroscopies, X-ray diffraction and conductometry. Uv–Vis and Raman spectra, supported by conductometric measurements, consistently indicate that the solubilized salt is present mostly as TBP n [FeCl3???n ] n+ and FeCl4 ? complex ions due to specific interaction with the TBP phosphate group. Thanks to this interaction, a high amount of salt (up to 13 % w/w) can be dissolved despite the relatively low dielectric constant of TBP. The X-ray diffractogram of pure TBP has been interpreted in terms of three main contributions which can be attributed to spatial pair correlations between atoms of interacting TBP molecules. In the presence of increasing FeCl3 amounts, it has been observed a progressive structuring effect, exerted by the dissolved salt, on the layers of opportunely oriented TBP molecules due to the formation of the complex ionic species. By simple treatment with NaBH4, the synthesis of Fe nanoparticles has been achieved. The absence of water, the easiness of preparation, the high amount of salt which can be suspended and the peculiar physico-chemical properties of such systems are all elements worth of note for the fields of nanoparticle synthesis and for specialized technological applications. 相似文献