全文获取类型
收费全文 | 769篇 |
免费 | 24篇 |
国内免费 | 3篇 |
专业分类
化学 | 461篇 |
晶体学 | 3篇 |
力学 | 75篇 |
数学 | 59篇 |
物理学 | 198篇 |
出版年
2023年 | 2篇 |
2022年 | 28篇 |
2021年 | 29篇 |
2020年 | 22篇 |
2019年 | 18篇 |
2018年 | 23篇 |
2017年 | 19篇 |
2016年 | 42篇 |
2015年 | 30篇 |
2014年 | 28篇 |
2013年 | 48篇 |
2012年 | 49篇 |
2011年 | 50篇 |
2010年 | 46篇 |
2009年 | 44篇 |
2008年 | 41篇 |
2007年 | 31篇 |
2006年 | 27篇 |
2005年 | 31篇 |
2004年 | 36篇 |
2003年 | 22篇 |
2002年 | 23篇 |
2001年 | 9篇 |
2000年 | 10篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 2篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 4篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1973年 | 2篇 |
1906年 | 1篇 |
排序方式: 共有796条查询结果,搜索用时 0 毫秒
1.
2.
3.
Margarete O. Machado 《Journal of Physics and Chemistry of Solids》2004,65(10):1697-1703
The crystalline lamellar compound, VOPO4·2H2O, was employed as host to react with a long monoamine aliphatic chain, dodecylamine, and with an aromatic derivative, nicotinamide, using two distinct synthetic approaches: in the solid state and from aqueous solution. The resulting compounds were characterized by elemental analysis, infrared spectroscopy, X-ray diffractometry, thermogravimetry and SEM microscopy. From X-ray diffraction patterns, the calculated increase of the interlayer distance was 2.05 nm for the dodecylamine, containing product, which is in agreement with the intercalation process, and was observed with both reactions routes. On the contrary, the guest nicotinamide molecule was not inserted into the lamellar cavity. The reaction in the solid state caused a small modification of the phosphate microstructure, in comparison with the solution procedure. The aliphatic amine molecules are oriented in a bilayer inside the host cavity by forming an angle of 67° with the inorganic lamella. The thermal decomposition for both series of synthesized compounds did not demonstrate any difference in behavior. 相似文献
4.
5.
P. A. V. Ferreira M. E. S. Machado 《Journal of Optimization Theory and Applications》1996,89(3):659-680
Projection and relaxation techniques are employed to decompose a multiobjective problem into a two-level structure. The basic manipulation consists in projecting the decision variables onto the space of the implicit tradeoffs, allowing the definition of a relaxed multiobjective master problem directly in the objective space. An additional subproblem tests the feasibility of the solution encountered by the relaxed problem. Some properties of the relaxed problem (linearity, small number of variables, etc.) render its solution efficient by a number of methods. Representatives of two different classes of multiobjective methods [the Geoffrion, Dyer, Feinberg (GDF) method and the fuzzy method of Baptistella and Ollero] are implemented and applied within this context to a water resources allocation problem. The results attest the computational viability of the overall procedure and its usefulness for the solution of multiobjective problems.This work was partially sponsored by grants from CNPq and FAPESP, Brazil. The authors are indebted to the anonymous reviewers for their valuable comments. 相似文献
6.
Electroanalytical and chromatographic determination of pentachlorophenol and related molecules in a contaminated soil: a real case example 总被引:1,自引:0,他引:1
L. Codognoto V. G. Zuin D. de Souza J. H. Yariwake S. A. S. Machado L. A. Avaca 《Microchemical Journal》2004,77(2):177-184
Electroanalytical and chromatographic methodologies have been applied for the determination of pentachlorophenol (PCP) and some of its derivatives in real soil samples contaminated by industrial discharge. The analytes were extracted with hexane from soil samples collected at different points of the site and mixed to produce a representative sample. Square wave voltammetry (SWV) experiments were carried out on either a boron-doped diamond (BDD) electrode or a gold ultramicroelectrode (Au-UME) in an analyte composed by the Britton-Robinson (B-R) buffer at pH 5.5 with the direct addition of proper amounts of the extract. The voltammetric responses revealed an irreversible anodic peak at approximately 0.80 V vs. Ag/AgCl with a peak current showing a linear dependence on PCP concentration. This linear relationship yielded a detection limit (DL) of 2×10−8 mol l−1 (or 5.5 μg l−1) for the BDD electrode and 6.9×10−8 mol l−1 (18.4 μg l−1) for the Au-UME, while the independently measured HPLC detection limit was 1.1×10−8 mol l−1 (3.0 μg l−1). The application of electroanalytical and chromatographic methodologies in the analysis of soil extracts revealed, besides the PCP responses, signals for some related molecules such as o-tetrachlorobenzoquinone (o-chloranil), hexachlorobenzene and tetrachlorophenol. Recovering experiments for PCP showed a concentration of 27.5 mg kg−1 for the electroanalytical determinations and 26.8 mg kg−1 for the HPLC analysis, values exceedingly high if considering that the maximum residue limit established for natural waters by the Brazilian Environmental Agency is 10 μg l−1. 相似文献
7.
Machado AM Wypych F Drechsel SM Nakagaki S 《Journal of colloid and interface science》2002,254(1):158-164
Two samples of montmorillonite (one of Brazilian origin, BNC1 clay, and the other STX-1, supplied by the Clay Mineral Society Repository (University of Missouri, USA) were allowed to react with biomimetic metalloporphyrins of Fe(III) and Mn(III) in cationic form. The compounds were characterized by several techniques, showing that the metalloporphyrins molecules were adsorbed at the surface of the clay platelet crystals. The catalytic activities of the intercalated complexes for the oxidation of alkane were dependent upon the concentration of the porphyrin immobilized in the clay and factors such as the metal ion species in the porphyrins, choice of solvent, and concentration of the iodosylbenzene oxidant. Good selectivity to cyclohexanol instead of cyclohexanone was observed for the catalytic oxidation of cyclohexane by iodosylbenzene. 相似文献
8.
The mathematical evaluation of the activation
energy, E, of non-isothermal degradation
reactions is usually made using the Ozawa/Flynn–Wall isoconversion principle
and involves the numerical resolution of a set of integrals without closed
form solution, which are solved by polynomial approximation or by numeric
integration. In the present work, the isoconversion principle, originally
described and maintained until now as an algebraic problem, was written as
a set of ordinary differential equations (ODEs). The individual ODEs obtained
are integrated by numeric methods and are used to estimate the activation
energy of simulated examples. A least square error (LSE) objective function
using the introduced ODEs was written to deal with multiple heating rate CaCO3
thermal decomposition TG experiments. 相似文献
9.
10.
Rubén A. Machado David Rivillo Lindora D’Ornelas Reinaldo Atencio Esperanza Galarza 《Journal of organometallic chemistry》2004,689(15):2486-2493
The reaction of the labile compound [Re2(CO)8(CH3CN)2] with trans-1,2-bis(2-pyridyl)ethene (C12H10N2) at room temperature in tetrahydrofuran affords the compounds [Re2(μ:η3-C12H10N2)(CO)8] (1) and the oxidative addition product [Re2(μ-H)(μ:η3-C12H9N2)(CO)7] (2). When the reaction is carried out at temperatures of refluxing tetrahydrofuran, besides compounds 1 and 2, the oxidative addition product [Re2(μ-H)(μ:η4-C12H9N2)(CO)6] (3), the insertion product [Re2(μ:η4-C12H10N2)(CO)8] (4) and [Re2(μ:η6-C24H18N4)(CO)6] (5) are obtained. Compound 5 contains the organic ligand rtct-tetrakis(2-pyridyl)cyclobutandiyl which is derived from a [2 + 2] cycloaddition of 1,2-bis(2-pyridyl)ethene mediated by its coordination to the bimetallic framework. The molecular structures of 1, 2, 4 and 5 were confirmed by X-ray crystallographic studies. 相似文献