全文获取类型
收费全文 | 210篇 |
免费 | 4篇 |
国内免费 | 5篇 |
专业分类
化学 | 133篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 4篇 |
物理学 | 75篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 2篇 |
2019年 | 5篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 3篇 |
2014年 | 5篇 |
2013年 | 5篇 |
2012年 | 7篇 |
2011年 | 16篇 |
2010年 | 12篇 |
2009年 | 7篇 |
2008年 | 9篇 |
2007年 | 11篇 |
2006年 | 12篇 |
2005年 | 8篇 |
2004年 | 9篇 |
2003年 | 10篇 |
2002年 | 9篇 |
2001年 | 5篇 |
2000年 | 10篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 4篇 |
1989年 | 7篇 |
1988年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有219条查询结果,搜索用时 15 毫秒
191.
The fragmentation of anomeric alkoxyl radicals (ARF) and the subsequent intramolecular cyclization promoted by hypervalent iodine reagents provide an excellent method for the synthesis of tetrazolo-sugars. This new reaction offers additional advantages for the synthesis of these compounds, including the ready availability of the starting materials, experimental simplicity, mild conditions, and good yields. 相似文献
192.
Muñoz-Rojas D Córdoba R Fernández-Pacheco A De Teresa JM Sauthier G Fraxedas J Walton RI Casañ-Pastor N 《Inorganic chemistry》2010,49(23):10977-10983
The silver-copper mixed oxide AgCuO(2) (also formulated as Ag(2)Cu(2)O(4)) possesses a peculiar electronic structure in which both Ag and Cu are partially oxidized, with the charge being delocalized among the three elements in the oxide. Accordingly, a quasi-metallic behavior should be expected for this oxide, and indeed bulk transport measurements show conductivity values that are orders of magnitude higher than for other members of this novel oxide family. The presence of silver makes thermal sintering an inadequate method to evaluate true conductivity, and thus such measurements were performed on low density pellets, giving an underestimated value for the conductivity. In the present work we present a new synthetic route for AgCuO(2) based on mild hydrothermal reactions that has yielded unprecedented large AgCuO(2) single-crystals well over 1 μm in size using temperatures as low as 88 °C. We have used a dual beam instrument to apply nanocontacts to those crystals, allowing the in situ measurement of transport properties of AgCuO(2) single crystals. The results show a linear relationship between applied current and measured voltage. The conductivity values obtained are 50 to 300 times higher than those obtained for bulk low density AgCuO(2) pellets, thus confirming the high conductivity of this oxide and therefore supporting the delocalized charge observed by spectroscopic techniques. 相似文献
193.
David Muñoz-Rojas Judith Oró-Solé Benjamín Martínez Jesús Canales-Vázquez Ester García-González Nieves Casañ-Pastor 《Journal of solid state chemistry》2006,179(12):3883-3892
The use of hydrothermal methods has allowed the synthesis of a new silver copper mixed oxide, Ag2CuMnO4, the first example of a quaternary oxide containing both elements. It crystallizes with the delafossite 3R structure, thus being the first delafossite to contain both Ag and Cu. Synthesis conditions affect the final particle size (30-500 nm). Powder X-ray diffraction Rietveld refinement indicates a trigonal structure and cell parameters and , where Cu and Mn are disordered within the octahedral B positions in the plane and linearly coordinated Ag occupies de A position between layers. X-ray absorption near edge spectroscopy (XANES) for copper and manganese, and XPS for silver evidence +2, +4, and +1 oxidation states. The microstructure consists of layered particles that may form large twins showing 5 nm nanodomains. Finally, magnetic measurements reveal the existence of ferromagnetic coupling yielding in-plane moments that align antiferromagnetically at lower temperatures. The singularity of the new phase resides on the fact that is an example of a bidimensional arrangement of silver and copper in an oxide that also shows clear bidimensionality in its physical properties. That is of special relevance to the field of high Tc superconducting oxides, while the ferromagnetic coupling in a bidimensional system deserves itself special attention. 相似文献
194.
Microwave-assisted solvent extraction of persistent organochlorine pesticides (POPs) in marine sediment was developed and optimized by means of two-level factorial designs. Six variables (microwave power, extraction time and temperature, amount of sample, solvent volume, and sample moisture) were considered as factors in the optimization process. The results show that the amount of sample to be extracted and solvent volume are statistically significant for the overall recovery of the studied pesticides, although compromise conditions have to be established with the object of avoiding overpressure in closed vessels. After extraction, a clean up step including the use of a silica cartridge was performed prior to chromatographic determination in order to remove interferences. The optimized procedure was compared to conventional Soxhlet extraction. The MS-MS ion preparation mode was applied to improve the sensitivity and selectivity of the chromatographic technique. 相似文献
195.
R. Santos-Ortiz E. Tupitsyn I. Nieves P. Bhattacharya A. Burger 《Journal of Crystal Growth》2011,314(1):293-297
AgGaxIn1?xSe2 single crystals with x=0.4 have been grown by the horizontal Bridgman technique for nonlinear optical application requires phase matching. High purity polycrystalline synthesis of AgGaxIn1?xSe2 was carried out at 850 °C, which is a relatively lower temperature compared to those in earlier reports, thus reducing secondary phase formation. An average Ga:In ratio of 62:38 (±3%) was measured using energy dispersive spectroscopy (EDS). As grown, a single crystal shows very high IR transmission of ~65% in the spectral range of 4000–600 cm?1. There was no significant change in its IR transmission after annealing it at 500 °C for 20 days in vacuum in the presence of AgGaxIn1?xSe2 powder. This indicates a low concentration of defects in the crystal. The results demonstrate that the improved new synthesis method for crystal growth was promising and that the quality of the crystal was good. 相似文献
196.
In this work turbidimetric and nephelometric techniques have been used to study the homocoagulation of aqueous dispersions
of uniform spherical particles of surfactant-free latexes. Cationic and anionic latexes of similar particle sizes (361 and
370 nm) and different surface charge densities (+16.4 and −3.6 μC/cm2) were used throughout. The kinetic constants which control the aggregation processes when the electrical repulsion disappears
were estimated by both techniques at different particle concentration and wavelength in order to establish the experimental
conditions which provided reliable and similar values for the coagulation rate constant. Both experimental techniques (turbidity
and nephelometry) and two ways of fitting the data have been used with both latexes. For the first method, the initial slope
of turbidity or total scattered intensity versus time curves were used to calculate the kinetic constants. In the second method,
the whole turbidity or total scattered intensity versus time curves were fitted and the kinetic constants calculated. An unambiguous
experimental value for the doublet rate constant in diffusion conditions is obtained by turbidity and nephelometry techniques.
By nephelometry both data treatments have permitted a distinction between the doublet rate constant and the global rate constant
in diffusion conditions.
Received: 2 June 1997 Accepted: 14 August 1997 相似文献
197.
198.
Summary The triglyceride composition of the Tempranillo grape (Vitis vinifera) has been examined by a combination of HPLC and GLC. To identify the triglycerides, equations were applied relating log k′
with the molecular variables: equivalent carbon number, chain length and number of double bonds in each of the fatty acids
in the glycerides. Ten triglycerides were found, the principal ones being trilinolein (35.75%), dilinoleyl-olein (21.03%)
and dilinoleyl-palmitin (17.02%). 相似文献
199.
A new physically adsorbed capillary coating for capillary electrophoresis-mass spectrometry (CE-MS) of basic proteins is presented, which is easily obtained by flushing the capillary with a polymer aqueous solution for two min. This coating significantly reduces the electrostatic adsorption of a group of basic proteins (i.e., cytochrome c, lysozyme, and ribonuclease A) onto the capillary wall allowing their analysis by CE-MS. The coating protocol is compatible with electrospray inonization (ESI)-MS via the reproducible separation of the standard basic proteins (%RSD values (n = 5) < 1% for analysis time reproducibility and < 5% for peak heights, measured from the total ion electropherograms (TIEs) within the same day). The LODs determined using cytochrome c with total ion current and extracted ion current defection were 24.5 and 2.9 fmol, respectively. Using this new coating lysozymes from chicken and turkey egg white could be easily distinguished by CE-MS, demonstrating the usefulness of this method to differentiate animal species. Even after sterilization at 120 degrees C for 30 min, lysozyme could be detected, as well as in wines at concentrations much lower than the limit marked by the EC Commission Regulation. Adulteration of minced meat with 5% of egg-white could also be analysed by our CE-MS protocol. 相似文献
200.