全文获取类型
收费全文 | 7905篇 |
免费 | 394篇 |
国内免费 | 2篇 |
专业分类
化学 | 5686篇 |
晶体学 | 68篇 |
力学 | 169篇 |
数学 | 956篇 |
物理学 | 1422篇 |
出版年
2023年 | 68篇 |
2022年 | 44篇 |
2021年 | 91篇 |
2020年 | 144篇 |
2019年 | 132篇 |
2018年 | 163篇 |
2017年 | 136篇 |
2016年 | 322篇 |
2015年 | 258篇 |
2014年 | 263篇 |
2013年 | 566篇 |
2012年 | 533篇 |
2011年 | 597篇 |
2010年 | 273篇 |
2009年 | 245篇 |
2008年 | 543篇 |
2007年 | 529篇 |
2006年 | 434篇 |
2005年 | 416篇 |
2004年 | 305篇 |
2003年 | 302篇 |
2002年 | 284篇 |
2001年 | 189篇 |
2000年 | 185篇 |
1999年 | 119篇 |
1998年 | 82篇 |
1997年 | 81篇 |
1996年 | 104篇 |
1995年 | 68篇 |
1994年 | 75篇 |
1993年 | 92篇 |
1992年 | 76篇 |
1991年 | 44篇 |
1990年 | 39篇 |
1989年 | 33篇 |
1988年 | 29篇 |
1987年 | 28篇 |
1986年 | 24篇 |
1985年 | 63篇 |
1984年 | 56篇 |
1983年 | 38篇 |
1982年 | 35篇 |
1981年 | 31篇 |
1980年 | 25篇 |
1979年 | 12篇 |
1978年 | 23篇 |
1977年 | 17篇 |
1976年 | 11篇 |
1975年 | 17篇 |
1974年 | 15篇 |
排序方式: 共有8301条查询结果,搜索用时 46 毫秒
181.
Determination of macrolide antibiotics by liquid chromatography 总被引:7,自引:0,他引:7
The liquid chromatographic separation of seven macrolides used in food producing animals in the European Union has been studied. Separation was performed by using an end-capped high-purity silica-based C18 column and mobile phases consisting of phosphate buffer (pH 2.5)–acetonitrile mixtures. The effect of pH and acetonitrile percentage on the separation was examined. Two UV-based detection systems, wavelength programming and diode array, were assayed. Detection limits were in the range 6–33 μg l−1 for spiramycin, tilmicosin, tylosin, kitasamicin and josamicin and about 400 μg l−1 for erythromycin and oleandomycin. The suitability of the method for multiresidue determination of the five macrolides is demonstrated by the analysis of spiked samples of chicken muscle. 相似文献
182.
An interface-free combination of HPLC separation techniques and methods for element determination by atomic spectrometry can be achieved by hydraulic high-pressure nebulization (HHPN). With high-temperature HHPN (300 ( degrees )C) super heated liquids can be nebulized providing aerosol yields of up to 90% in flame AAS. This new nebulization method combines the advantages of HHPN and thermospray techniques (very small aerosol droplets, high aerosol yield, nebulization of saturated salt solutions). 相似文献
183.
We show that the exact non-Born-Oppenheimer Schrodinger equation for the Hookean diatomic molecule H2 (a two-proton, two-electron system where the electron-proton interaction is harmonic while the proton-proton and electron-electron interactions are Coulombic) can be decoupled into equations describing the relative motion of the electrons, the relative motion of nuclei, the motion of a collective mode representing a three-dimensional harmonic oscillator, and the motion of a free particle expressed as a linear combination of the individual center-of-mass coordinates of the nuclei and electrons. Analytic solutions to the relative motion of electrons can be readily obtained for the given values of the harmonic coupling constant. However, exact analytic solutions to the equation for the relative motion of the nuclei cannot be obtained simultaneously due to the fact that the harmonic constants in these two equations are coupled. For this reason, we present for the relative nuclear motion approximate analytic wave functions, one of them obtained variationally and the other by a series solution where the coefficients are determined recursively. We also explore a variational solution to the Taylor-series expansion of the nuclear interaction potential. Properties of the electronic and nuclear intracule densities are examined at different values of the coupling constant. An interesting result of the present non-Born-Oppenheimer treatment of this harmonic model is the fact that the relative nuclear motion occurs in a highly correlated regime. This leads in a natural way to a spatial localization of the nuclei akin to Wigner electronic crystallization. 相似文献
184.
Martí S Andrés J Moliner V Silla E Tuñón I Bertrán J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(4):984-991
In this paper a deeper insight into the chorismate-to prephenate-rearrangement, catalyzed by Bacillus subtilis chorismate mutase, is provided by means of a combination of statistical quantum mechanics/molecular mechanics simulation methods and hybrid potential energy surface exploration techniques. The main aim of this work is to present an estimation of the preorganization and reorganization terms of the enzyme catalytic rate enhancement. To analyze the first of these, we have studied different conformational equilibria of chorismate in aqueous solution and in the enzyme active site. Our conclusion is that chorismate mutase preferentially binds the reactive conformer of the substrate--that presenting a structure similar to the transition state of the reaction to be catalyzed--with shorter distances between the carbon atoms to be bonded and more diaxial character. With respect to the reorganization effect, an energy decomposition analysis of the potential energies of the reactive reactant and of the reaction transition state in aqueous solution and in the enzyme shows that the enzyme structure is better adapted to the transition structure. This means not only a more negative electrostatic interaction energy with the transition state but also a low enzyme deformation contribution to the energy barrier. Our calculations reveal that the structure of the enzyme is responsible for stabilizing the transition state structure of the reaction, with concomitant selection of the reactive form of the reactants. This is, the same enzymatic pattern that stabilizes the transition structure also promotes those reactant structures closer to the transition structure (i.e., the reactive reactants). In fact, both reorganization and preorganization effects have to be considered as the two faces of the same coin, having a common origin in the effect of the enzyme structure on the energy surface of the substrate. 相似文献
185.
Alejandro Marcó Ramón Compañó Roser Rubio Pilar Domènech Albert Palangues Miguel Maestro 《Mikrochimica acta》2002,140(1-2):131-139
Four inter-comparison exercises on organic elemental analysis were carried out between 1997 and 2001 by the Department of
Analytical Chemistry of the University of Barcelona, together with the Microanalysis Service and the Institute of the Marine
Sciences, which both belong to the CSIC in Barcelona, and the University of A Coru?a. More than sixty laboratories participated
in these exercises. Here we describe the design and characteristics of the trials, the samples and the homogeneity tests applied.
We report the results obtained for the analysis of carbon, hydrogen, nitrogen, sulphur and oxygen, their statistical analysis,
and the most relevant aspects of the technical discussion meetings.
Received December 20, 2001; accepted March 18, 2002; published online July 22, 2002 相似文献
186.
Fast neutrons of 14 MeV produced in the IMICAM CISE 150-kV generator by the (d, t) reaction in a tritium-titanium target, were used in the indirect determination of Al(2)O(3). The samples were irradiated for 30 sec and the total (16)N activity was determined, by counting for ten 2-sec periods and graphically integrating. The standards were a known sintered aluminium powder and nylon pieces of identical shape. The method is competitive with the chemical one, because of its quickness, sensitivity and precision. 相似文献
187.
Justicia J Rosales A Buñuel E Oller-López JL Valdivia M Haïdour A Oltra JE Barrero AF Cárdenas DJ Cuerva JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(7):1778-1788
The titanocene-catalyzed cascade cyclization of epoxypolyenes, which are easily prepared from commercially available polyprenoids, has proven to be a useful procedure for the synthesis of C(10), C(15), C(20), and C(30) terpenoids, including monocyclic, bicyclic, and tricyclic natural products. Both theoretical and experimental evidence suggests that this cyclization takes place in a nonconcerted fashion via discrete carbon-centered radicals. Nevertheless, the termination step of the process seems to be subjected to a kind of water-dependent control, which is unusual in free-radical chemistry. The catalytic cycle is based on the use of the novel combination Me(3)SiCl/2,4,6-collidine to regenerate the titanocene catalyst. In practice this procedure has several advantages: it takes place at room temperature under mild conditions compatible with different functional groups, uses inexpensive reagents, and its end step can easily be controlled to give exocyclic double bonds by simply excluding water from the medium. 相似文献
188.
Barluenga J Diéguez A Rodríguez F Flórez J Fañanás FJ 《Journal of the American Chemical Society》2002,124(31):9056-9057
Eight-membered carbocycles with up to five new stereogenic centers are enantioselectively obtained following a one-pot procedure that involves the coupling of three components: an alkenyl Fischer carbene complex, a ketone enolate, and allyl lithium. 相似文献
189.
Lapeña AM Gross AF Tolbert SH 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):470-480
In this work, we examine the role of curvature and surfactant packing in controlling the structure of periodic silica/surfactant composites by driving such materials through a transformation from a hexagonal to a lamellar phase. We focus on how the interplay of desired packing and volume constraints dictates the resulting structures. In general, surfactants expand in a complex way upon heating, and this can cause a change in the optimal packing geometry. However, the presence of a rigid silica framework may prevent surfactants from reaching this preferred volume and/or curvature. Real-time in situ X-ray diffraction is used to monitor the structural evolution of these materials heated under hydrothermal treatments. Because the thermal-driven disorder of the surfactant tails drives the phase transition, we examine four types of composites with varying tail density. Ordinarily, composites consist of surfactants with one 20-carbon tail and one positively charged ammonium headgroup. Tail density is varied by replacing a small amount (0-16%) of these single-tail, single-head surfactants with single-tail, double-head 'gemini' surfactants. A greater head--tail ratio indeed produces different results, causing the phase transition to occur at higher temperatures. Using simple geometric models to gain better understanding of our experimental results, we find that, while both unfavorable curvature and limited volume may exist for the surfactants in these composites, the constrained curvature appears to be the dominant effect in driving structural rearrangement. 相似文献
190.
M. C. Mahedero A. Muñoz De La Peña A. Bautista J.J. Aaron 《Journal of inclusion phenomena and macrocyclic chemistry》2002,42(1-2):61-70
The effect of -cyclodextrin (-CD) and hydroxypropyl--cyclodextrin (HP--CD) upon the photochemically-induced fluorescence (PIF) properties of four phenylurea herbicides, including linuron, diuron, isoproturon and neburon has been studied. Photochemical conversion of these nonfluorescent herbicides into strongly fluorescent photoproducts was shown to occur in -CD and HP--CD aqueous media. The influence of pH, UV irradiation time and photoproduct stability on the fluorescence intensity was also investigated. In addition, the stoichiometry and formation constants of the complexes formed between herbicides and -cyclodextrin (-CD) or 2-hydroxypropyl--cyclodextrin (HP--CD) were determined. The formation constant values, ranging from 184 ± 40 to 1498 ± 245 M-1, were calculated by applying the iterative nonlinear regression (NLR) approach to the PIF data. Linear calibrations graphs were established in the interval 1–12 g/mL, for diuron, linuron and neburon. The IUPAC limits of detection ranged between 580 and 700 ng/mL, according to the compound. Application to the analysis of phenylurea herbicides in spiked river water was also described. 相似文献