全文获取类型
收费全文 | 454篇 |
免费 | 27篇 |
专业分类
化学 | 392篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 34篇 |
物理学 | 46篇 |
出版年
2023年 | 5篇 |
2022年 | 12篇 |
2021年 | 22篇 |
2020年 | 14篇 |
2019年 | 14篇 |
2018年 | 11篇 |
2017年 | 16篇 |
2016年 | 22篇 |
2015年 | 13篇 |
2014年 | 26篇 |
2013年 | 33篇 |
2012年 | 31篇 |
2011年 | 38篇 |
2010年 | 21篇 |
2009年 | 24篇 |
2008年 | 37篇 |
2007年 | 14篇 |
2006年 | 15篇 |
2005年 | 30篇 |
2004年 | 22篇 |
2003年 | 12篇 |
2002年 | 9篇 |
2001年 | 7篇 |
2000年 | 2篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1988年 | 3篇 |
1985年 | 1篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1979年 | 1篇 |
1977年 | 2篇 |
排序方式: 共有481条查询结果,搜索用时 343 毫秒
101.
The Effect of the Modification of Carbon Spheres with ZnCl2 on the Adsorption Properties towards CO2
Iwona Peech Piotr Staciwa Daniel Sibera Ewelina Kusiak-Nejman Antoni W. Morawski Joanna Kapica-Kozar Urszula Narkiewicz 《Molecules (Basel, Switzerland)》2022,27(4)
Zinc chloride and potassium oxalate are often applied as activating agents for carbon materials. In this work, we present the preparation of ZnO/carbon spheres composites using resorcinol-formaldehyde resin as a carbon source in a solvothermal reactor heated with microwaves. Zinc chloride as a zinc oxide source and potassium oxalate as an activating agent were applied. The effect of their addition and preparation conditions on the adsorption properties towards carbon dioxide at 0 °C and 25 °C were investigated. Additionally, for all tested sorbents, the CO2 sorption tests at 40 °C, carried out utilizing a thermobalance, confirmed the trend of sorption capacity measured at 0 and 25 °C. Furthermore, the sample activated using potassium oxalate and modified using zinc chloride (a carbon-to-zinc ratio equal to 10:1) displayed not only a high CO2 adsorption capacity (2.69 mmol CO2/g at 40 °C) but also exhibited a stable performance during the consecutive multicycle adsorption–desorption process. 相似文献
102.
We propose an incomplete split plot design where levels of one factor (say A) are applied to the wholeplots and levels of the other (say B) to subplots, and where the number of subplots in each wholeplot may be less than the number of levels of factor B.The t levels of factor A are arranged in a completely randomized design. The s levels of factor B are arranged in a connected and proper incomplete block design within each level of factor A, by considering the wholeplots as blocks. 相似文献
103.
Kanderal OM Kozlowski H Dobosz A Swiatek-Kozlowska J Meyer F Fritsky IO 《Dalton transactions (Cambridge, England : 2003)》2005,(8):1428-1437
Oxime ligands are able to form stable binuclear species with copper(II) ions in aqueous solution. They also have a strong tendency to decrease the Mn+/(n-1)+ redox potentials of the central ions. Ligands possessing the hydroxyimino groups together with other powerful sigma-donor groups can be very efficient chelating agents able to facilitate the stabilisation of high oxidation states of 3d-metals. Here we report the synthesis, structural characterization and redox behaviour of mononuclear and binuclear complexes based on hydroxyiminoamide tetradentate open-chain ligands. In all mononuclear anionic complexes the central atom is situated in a square-planar surrounding of four nitrogen atoms. This pseudo-macrocyclic conformation is due to the presence of short intramolecular hydrogen bonds uniting the cis-oximate oxygen atoms. The square-planar surrounding of the strong sigma-donors facilitates efficient stabilization of the trivalent state of copper and nickel ions. In cyclic voltammetry studies the quasi-reversible processes M2+-->M3+ can be observed. In the binuclear complexes the coordinatively saturated octahedral ion M[prime or minute] is bound to the two oxygen atoms of the bridging oximate groups and the four nitrogen atoms of the tetradentate ligand tren. Two metal ions (M and M') are linked by the double cis-oximate bridge and are incorporated in a six-membered bimetallic chelate ring. Metallamacrocycle formation leads to certain changes in the structural parameters of the binuclear complexes as compared to those observed in the mononuclear species. Also the study of the electrochemical activity of binuclear complexes has shown important differences in their redox behaviour as compared to their mononuclear precursors. 相似文献
104.
Berdys J Anusiewicz I Skurski P Simons J 《Journal of the American Chemical Society》2004,126(20):6441-6447
Although electrons having enough energy to ionize or electronically excite DNA have long been known to cause strand breaks (i.e., bond cleavages), only recently has it been suggested that even lower-energy electrons (most recently 1 eV and below) can also damage DNA. The findings of the present work suggest that, while DNA bases can attach electrons having kinetic energies in the 1 eV range and subsequently undergo phosphate-sugar O-C sigma bond cleavage, it is highly unlikely (in contrast to recent suggestions) that electrons having kinetic energies near 0 eV can attach to the phosphate unit's P=O bonds. Electron kinetic energies in the 2-3 eV range are required to attach directly to DNA's phosphate group's P=O pi orbital and induce phosphate-sugar O-C sigma bond cleavages if the phosphate groups are rendered neutral (e.g., by nearby counterions). Moreover, significant activation barriers to C-O bond breakage render the rates of both such damage mechanisms (i.e., P=O-attached and base-attached) slow as compared to electron autodetachment and to other damage processes. 相似文献
105.
Spectrochemical Properties of Cobalt(II) Complex with Bidentate Schiff Base in Various Solvents 总被引:1,自引:0,他引:1
Krzysztof Kurzak Iwona Kuźniarska-Biernacka Bogumila Żurowska 《Journal of solution chemistry》1999,28(2):133-151
As a continuation of our previous studies on copper(II) complexes with a bidentate Schiff base derived from 5-bromosalicylaldehyde and -aminopyridine, we have investigated the electronic spectra of the cobalt(II) complex with this ligand. The complex is a red crystalline compound soluble in common solvents, such as chloroform, dioxane, dimethyl formamide, dimethyl sulfoxide, and methanol. The time-elapsed spectral measurements of the complex and ligand, as well as conductivities of the complex in chloroform and dioxane solutions, are presented and discussed. Molar conductivities indicate that the complex exists as a nonelectrolyte in nonpolar solvents and as a 1:1 or 1:2 electrolyte in polar solvents. The ligand-field parameters (CFM/AOM) for the complex in chloroform solution are estimated and discussed. 相似文献
106.
107.
Iwona Włoch Urszula Bednarz Dorota Bród Andrzej Włoch Małgorzata Wołowiec-Musiał 《Discrete Applied Mathematics》2013,161(16-17):2695-2701
In this paper, we define a new kind of Fibonacci numbers generalized in the distance sense. This generalization is related to distance Fibonacci numbers and distance Lucas numbers, introduced quite recently. We also study distinct properties of these numbers for negative integers. Their representations and interpretations in graphs are also studied. 相似文献
108.
109.
Krzesimir Korona Michał Terlecki Dr. Iwona Justyniak Michał Magott Dr. Jan Żukrowski Dr. Arkadiusz Kornowicz Prof. Dawid Pinkowicz Prof. Adam Kubas Prof. Janusz Lewiński 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(40):e202200620
Paddlewheel-type binuclear complexes featuring metal−metal bonding have been the subject of widespread interest due to fundamental concern in their electronic structures and potential applications. Here, we explore the molecular and electronic structures of diiron(II,II) complexes with N,N’-diarylformamidinate ligands. While a paddlewheel-type diiron(II,II) complex with N,N’-diphenylformamidinate ligands (DPhF) exhibits the centrosymmetric [Fe2(μ-DPhF)4] structure, a minor alteration in the ligand system, i. e., switching from phenyl to p-tolyl N-substituted formamidinate ligand (DTolF), resulted in the isolation of an unprecedented non-centrosymmetric [Fe(μ-DTolF)3Fe(κ2-DTolF)] complex. Both complexes were characterized using single-crystal X-ray diffraction, magnetic measurements, 57Fe Mössbauer spectroscopy, and cyclic voltammetry along with high-level ab-initio calculations. The results provide a new view on a range of factors controlling the ground-state electronic configuration and structural diversity of homoleptic diiron(II,II) complexes. Model calculations determined that the Mayer bond orders for Fe−Fe interactions are significantly lower than 1 and equal to 0.15 and 0.28 for [Fe2(μ-DPhF)4] and [Fe(μ-DTolF)3Fe(κ2-DTolF)], respectively. 相似文献
110.