全文获取类型
收费全文 | 422篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 269篇 |
晶体学 | 2篇 |
力学 | 4篇 |
数学 | 89篇 |
物理学 | 70篇 |
出版年
2023年 | 2篇 |
2022年 | 8篇 |
2021年 | 6篇 |
2020年 | 20篇 |
2019年 | 14篇 |
2018年 | 10篇 |
2017年 | 4篇 |
2016年 | 14篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 28篇 |
2012年 | 36篇 |
2011年 | 28篇 |
2010年 | 19篇 |
2009年 | 23篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 18篇 |
2005年 | 20篇 |
2004年 | 12篇 |
2003年 | 11篇 |
2002年 | 11篇 |
2001年 | 9篇 |
1999年 | 1篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 1篇 |
1995年 | 6篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 3篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1966年 | 1篇 |
1960年 | 1篇 |
1958年 | 1篇 |
排序方式: 共有434条查询结果,搜索用时 15 毫秒
161.
162.
Studies of trace metal mobilization in sediments are generally performed using sequential extraction schemes at equilibrium. In the present work, a kinetic fractionation of trace metals in sediments has been developed to assess that information. The extraction rate data have been obtained using a single extraction scheme with EDTA and following a protocol previously optimized. Two kinetic equations and two kinetic models were used to fit the experimental data. The two constants equation fits well the extraction rate data used in this work but does not present any physico-chemical meaning. The diffusion model and the two first-order reactions model allow determining which parameter (the reaction between the metal M and the EDTA or the diffusion of the complex M/EDTA) is rate limiting in the trace metal extraction by EDTA. It appears that the two first-order reactions model is more efficient than the diffusion model to fit the present extraction rate data so it can be deduced that the diffusion of the complex M/EDTA is not the limiting step of the trace metal extraction by EDTA in estuarine sediments. In a second part, relationships between the fraction of metals determined with the two first-order reactions model and the sediments composition were established. 相似文献
163.
Belyakov AV Kieninger M Cachau RE Ventura ON Oberhammer H 《The journal of physical chemistry. A》2005,109(2):394-399
The geometric structure of 2,3,5,6-tetrafluoroanisole and the potential function for internal rotation around the C(sp2)-O bond were determined by gas electron diffraction (GED) and quantum chemical calculations. Analysis of the GED intensities with a static model resulted in near-perpendicular orientation of the O-CH3 bond relative to the benzene plane with a torsional angle around the C(sp2)-O bond of tau(C-O) = 67(15) degrees. With a dynamic model, a wide single-minimum potential for internal rotation around the C(sp2)-O bond with perpendicular orientation of the methoxy group [tau(C-O) = 90 degrees] and a barrier of 2.7 +/- 1.6 kcal/mol at planar orientation [tau(C-O) = 0 degrees] was derived. Calculated potential functions depend strongly on the computational method (HF, MP2, or B3LYP) and converge adequately only if large basis sets are used. The electronic energy curves show internal structure, with local minima appearing because of the interplay between electron delocalization, changes in the hybridization around the oxygen atom, and the attraction between the positively polarized hydrogen atoms in the methyl group and the fluorine atom at the ortho position. The internal structure of the electronic energy curves mostly disappears if zero-point energies and thermal corrections are added. The calculated free energy barrier at 298 K is 2.0 +/- 1.0 kcal/mol, in good agreement with the experimental determination. 相似文献
164.
We have studied the hydration and diffusion of the hydroxyl radical OH0 in water using classical molecular dynamics. We report the atomic radial distribution functions, hydrogen-bond distributions, angular distribution functions, and lifetimes of the hydration structures. The most frequent hydration structure in the OH0 has one water molecule bound to the OH0 oxygen (57% of the time), and one water molecule bound to the OH0 hydrogen (88% of the time). In the hydrogen bonds between the OH0 and the water that surrounds it the OH0 acts mainly as proton donor. These hydrogen bonds take place in a low percentage, indicating little adaptability of the molecule to the structure of the solvent. All hydration structures of the OH0 have shorter lifetimes than those corresponding to the hydration structures of the water molecule. The value of the diffusion coefficient of the OH0 obtained from the simulation was 7.1x10(-9) m2 s(-1), which is higher than those of the water and the OH-. 相似文献
165.
William H. Miller Thomas W. Ku Fadia E. Ali William E. Bondinell Raul R. Calvo Larry D. Davis Karl F. Erhard Leon B. Hall William F. Huffman Richard M. Keenan Chet Kwon Kenneth A. Newlander Stephen T. Ross James M. Samanen Dennis T. Takata Chuan-Kui Yuan 《Tetrahedron letters》1995,36(52):9433-9436
An enantiospecific synthesis of SB 214857, a potent, nonpeplide fibrinogen receptor antagonist, is reported. The synthetic route employs as a key step an intramolecular aryl fluoride displacement to form the sevenmembered ring of the 1,4-benzodiazepine system. 相似文献
166.
Frederico?Cunha J.?Raul?Garcia Francisco?C.?NartEmail author Paola?Corio Márcia?Temperini 《Journal of Solid State Electrochemistry》2003,7(9):576-581
The potential-induced changes in thymine coordination on polycrystalline silver electrodes are studied by surface enhanced Raman spectroscopy (SERS) for potentials positive to the potential of zero charge up to the end of the double layer range. Two distinct sets of spectra could be obtained in the range of potentials studied. Both states correspond to chemisorbed phases of thymine on silver, where a distinct heteroatom is deemed responsible for the bond with the surface. At less positive potentials, one of the ring oxygen atoms is responsible for the chemical bond and the molecule assumes a tilted position. At more positive potentials, one of the ring nitrogen atoms, possibly deprotonated, establishes a new bond with the surface, aligning the molecule's axis closer to the surface normal.This paper is dedicated to Prof. Wolf Vielstich on the occasion of his 80th birthday for his outstanding contributions to electrochemistry 相似文献
167.
Toscano Ruben A. Rosas Raul Hernandez-Galindo Maria del Carmen Alvarez-Toledano Cecilio Garcia-Mellado Olivia 《Transition Metal Chemistry》1998,23(2):113-116
Transition Metal Chemistry - 相似文献
168.
169.
Calvo R Rapp RE Chagas E Sartoris RP Baggio R Garland MT Perec M 《Inorganic chemistry》2008,47(22):10389-10397
Three isostructural Cu 2Ln 2 1-D polymers [Cu 2Ln 2L 10(H 2O) 4.3H 2O] n where Ln = Gd ( 1), Er ( 2), and Y ( 3) and HL= trans-2-butenoic acid, were synthesized and characterized by X-ray crystallography, electron paramagnetic resonance, and magnetic measurements. Pairs of alternate Cu 2 and Ln 2 dinuclear units are combined into a linear array by a set of one covalent eta (2):eta (1):mu 2 carboxylate oxygen and two H bonds, at Cu...Ln distances of ca. 4.5 A. These units exhibit four eta (1):eta (1):mu 2 and two eta (2):eta (1):mu 2 carboxylate bridges, respectively. Magnetic measurements between 2 and 300 K, fields B 0 = mu 0 H between 0 and 9 T, and electron paramagnetic resonance (EPR) measurements at the X-band and room temperature are reported. The magnetic susceptibilities indicate bulk antiferromagnetic behavior of the three compounds at low temperatures. Magnetization and EPR data for 1 and 3 allowed evaluation of the exchange couplings between both Cu and Gd ions in their dinuclear units and between Cu and Gd neighbor ions in the spin chains. The data for the isolated Cu 2 units in 3 yield g || = 2.350 and g [symbol: see text] = 2.054, J Cu-Cu = -338 (3) cm (-1) for the exchange coupling [ H ex(1,2) = - J 1-2 S1 x S2], and D 0 = -0.342 (0.003) cm (-1) and E 0 = 0.003 (0.001) cm (-1) for the zero-field-splitting parameters of the triplet state arising from anisotropic spin-spin interactions. Considering tetranuclear blocks Gd-Cu-Cu-Gd in 1, with the parameters for the Cu 2 unit obtained for 3, we evaluated ferromagnetic interactions between Cu and Gd neighbors, J Cu-Gd = 13.0 (0.1) cm (-1), and between Gd ions in the Gd 2 units, J Gd-Gd = 0.25 (0.02) cm (-1), with g Gd = 1.991. The bulk antiferromagnetic behavior of 1 is a consequence of the antiferromagnetic coupling between Cu ions and of the magnitude, |J Cu-Gd|, of the Cu-Gd exchange coupling. Compound 2 displays a susceptibility peak at 15 K that may be interpreted as the combined result from antiferromagnetic couplings between Er (III) ions in Er 2 units and their coupling with the Cu 2 units. 相似文献
170.
Manaa MR Mitchell AR Garza RG Pagoria PF Watkins BE 《Journal of the American Chemical Society》2005,127(40):13786-13787
Optical ignition and initiation of energetic materials could thus far be only accomplished through lasers, with specific characteristics of high power, pulse length, wavelength, and a small target area that greatly inhibit their applications. Here, we report that an ignition and an initiation process, further leading to actual detonation, does occur for energetic materials in lax contact with carbon nanotubes that are prone to opto-thermal activity via a conventional flashbulb. Our results show that, for the first time, optical initiation of energetic materials is possible on a large surface area and using ordinary light intensity of several W/cm2. The implication is that energetic materials mixed with optically active nanotubes could be new ideal candidates for safety apparatus, such as the firing of bolts on space shuttle rockets and aircraft exit doors. 相似文献