全文获取类型
收费全文 | 2939篇 |
免费 | 102篇 |
国内免费 | 19篇 |
专业分类
化学 | 2087篇 |
晶体学 | 15篇 |
力学 | 61篇 |
数学 | 322篇 |
物理学 | 575篇 |
出版年
2023年 | 15篇 |
2022年 | 31篇 |
2021年 | 49篇 |
2020年 | 35篇 |
2019年 | 51篇 |
2018年 | 34篇 |
2017年 | 34篇 |
2016年 | 74篇 |
2015年 | 77篇 |
2014年 | 83篇 |
2013年 | 164篇 |
2012年 | 171篇 |
2011年 | 182篇 |
2010年 | 116篇 |
2009年 | 114篇 |
2008年 | 180篇 |
2007年 | 161篇 |
2006年 | 138篇 |
2005年 | 147篇 |
2004年 | 133篇 |
2003年 | 93篇 |
2002年 | 108篇 |
2001年 | 55篇 |
2000年 | 78篇 |
1999年 | 32篇 |
1998年 | 46篇 |
1997年 | 30篇 |
1996年 | 27篇 |
1995年 | 43篇 |
1994年 | 37篇 |
1993年 | 35篇 |
1992年 | 37篇 |
1991年 | 39篇 |
1990年 | 36篇 |
1989年 | 25篇 |
1988年 | 28篇 |
1987年 | 21篇 |
1986年 | 23篇 |
1985年 | 31篇 |
1984年 | 38篇 |
1983年 | 25篇 |
1982年 | 22篇 |
1981年 | 24篇 |
1980年 | 13篇 |
1979年 | 10篇 |
1978年 | 9篇 |
1977年 | 16篇 |
1976年 | 10篇 |
1975年 | 9篇 |
1974年 | 9篇 |
排序方式: 共有3060条查询结果,搜索用时 15 毫秒
111.
Elayaraja Muthuswamy S. Sree Ramadevi H.N. Vasan Cécile Garcia Laure Noé Marc Verelst 《Journal of nanoparticle research》2007,9(4):561-567
A novel synthesis of inorganic–organic hybrid films containing well dispersed and almost uniform size Ag nanoparticles in
agar-agar matrix has been reported. The films are found to be highly stable for more than a year. The colloidal particles
of Ag can be obtained in large quantities in the form of a film or in the gel form when dispersed in agar-agar or by dissolving
in a suitable solvent as solution. Characterization has been done by UV–visible spectroscopy and TEM. The hybrid may be of
interest to study third-order non-linear susceptibility. 相似文献
112.
In polymer films carrying an excess of fixed charge the electrostatic penalty to bring ions of same charge from the bathing electrolyte into the film sets a membrane potential (Donnan Potential) across the film-electrolyte interface. This potential is responsible for the ionic permselectivity observed in polyelectrolyte membranes. We have used electrochemical measurements to probe the dependence of the Donnan potential on the acid-base equilibrium in layer-by-layer self-assembled polyelectrolyte multilayers. The voltammperogram peak position of the Os(III)/Os(II) couple in self-assembled polyelectrolyte multilayers comprised of poly(allylamine) derivatized with Os(bpy)(2)PyCl+ and poly(vinylsulfonate) was recorded in solutions of increasing ionic strength for different assembly and testing solution pH. Protonation-deprotonation of the weak redox poly(allylamine) changes the fixed charge population in the as prepared (intrinsic) self-assembled redox polyelectrolyte multilayers. For films assembled in solutions of pH higher than the test solution pH, the Donnan plots (E(app) vs log C) exhibit a negative slope (anionic exchanger) while for films assembled at lower pH than that of the test solution positive slopes (cationic exchanger) are apparent. The ion exchange mechanism has been supported by complementary electrochemical quartz crystal microbalance. X-ray photoelectron spectroscopy and infrared reflection-absorption spectroscopy experiments demonstrated that the as prepared films have a memory effect on their protonation state during assembly, which leads to the observed dependence of the Donnan potential on the adsorption pH. 相似文献
113.
114.
Daniel M. Reis Ernesto Reyes‐Gómez Luiz E. Oliveira Carlos A. A. de Carvalho 《Annalen der Physik》2018,530(7)
The electromagnetic propagation in a relativistic electron gas at finite temperatures and carrier densities is described. Using quantum electrodynamics at finite temperatures, electric and magnetic responses and general constitutive relations are obtained. Rewriting the propagator for the electromagnetic field in terms of the electric and magnetic responses, the modes that propagate in the gas are identified. As expected, the usual collective excitations are obtained, i.e., a longitudinal electric and two transverse magnetic plasmonic modes. In addition, a purely photonic mode is found, which satisfies the wave equation in vacuum, for which the electron gas is transparent. Dispersion relations for the plasmon modes at zero and finite temperatures are presented and the intervals of frequency and wavelength where both electric and magnetic responses are simultaneously negative are identified, a behavior previously thought not to occur in natural systems. The investigation of the electromagnetic responses of a relativistic electron gas shows that, apart from the usual longitudinal electric plasmon mode and the two transverse magnetic plasmon modes, there is also a pure photonic mode that propagates with the speed of light, as if the medium were transparent. Furthermore, there is a region of frequencies and wavenumbers of the external fields where both the longitudinal electric permittivity and magnetic permeability are simultaneously negative, a property found in artificially constructed metamaterials. 相似文献
115.
Eric Steiner Carl Djerassi Ernesto Fattorusso Silvana Magno Luciano Mayol Circo Santacroce Donato Sica 《Helvetica chimica acta》1977,60(2):475-481
Two acetylenic steroids, cholest-5-en-23-yn-3β-ol ( 5 ) and 26,27-dinorcholest-5-en-23-yn-3β-ol ( 3 ), and another unsaturated steroidalcohol, stigmasta-5,23-dien-3β-ol ( 7 ), were isolated from the sponge Calyx nicaaensis. The structures of these two acetylenic steroids were established by synthesis. Several attempts to synthesize the marine steroids alcohol calysterol ( 1 ), with a cyclopropene-containing side chain, starting from cholest-5-en-23-yn-3β-ol are also recorded. Addition of ethyl-diazo-acetate to the triple bond was performed, but the reduction to the methyl derivative yielded decomposition products. 相似文献
116.
A method is described for the determination of molybdenum down to the microgram level, in samples of soil, steels, fertilizers and pharmaceuticals. After attack with acids, this element is separated from matrix elements by extraction of its 5,5'-methylenedisalicylohydroxamic acid (MEDSHA) complex from 4M hydrochloric acid, into methyl isobutyl ketone. Molybdenum is determined by atomic-absorption spectrometry (AAS), after conversion of the Mo-MEDSHA complex into the MoSCN(-) complex in the organic phase. The detection limit is 0.03 microg/ml, with a relative standard deviation not exceeding 1.5% at a level of 2 microg/ml. The method is highly selective and suffers only from interference by tungsten. 相似文献
117.
Alvaro M Atienzar P de la Cruz P Delgado JL Troiani V Garcia H Langa F Palkar A Echegoyen L 《Journal of the American Chemical Society》2006,128(20):6626-6635
A soluble, functionalized Py-SWNT has been synthesized and characterized by solution (1)H and (13)C NMR, FT-Raman, and electron microscopy. Experimental data indicate that Py-SWNT has short tubes with pentyl esters at the tips and pyridyl isoxazolino units along the walls. The synthesis of Py-SWNT is based on a 1,3-dipolar cycloaddition of a nitrile oxide on the SWNT walls, similar to 1,3-dipolar cycloadditions that are common for fullerene functionalization. The resulting Py-SWNT forms a complex with a zinc porphyrin (ZnPor) in a way similar to that reported for pyridyl-functionalized [60]-fullerenes. Formation of this metal-ligand complex was firmly established by a detailed electrochemical study. However, in contrast to the behavior observed for the ZnPor/Py-C(60) complex, photochemical excitation of the complex between ZnPor/Py-SWNT does not lead to electron transfer with the generation of charge-separated states. Fluorescence and laser flash studies indicate that the main process is energy transfer from the singlet ZnPor excited state to the Py-SWNT with observation of emission from Py-SWNT. Triplet ZnPor excited-state quenching by Py-SWNT is only observed in polar solvents such as DMF, but not in benzonitrile. 相似文献
118.
M.E. Garcia H.O. Jeschke I. Grigorenko K.H. Bennemann 《Applied physics. B, Lasers and optics》2000,71(3):361-371
We present a theoretical study of the short-time relaxation of clusters in response to ultrafast excitations using femtosecond
laser pulses. We analyze the excitation of different types of clusters (Hgn, Agn, Sin, C60 and Xen) and classify the relaxation dynamics in three different regimes, depending on the intensity of the exciting laser pulse.
For low-intensity pulses (I<1012 W/cm2) we determine the time-dependent structural changes of clusters upon ultrashort ionization and photodetachment. We also study
the laser-induced non-equilibrium fragmentation and melting of Sin and C60 clusters, which occurs for moderate laser intensities, as a function of the pulse duration and energy.
As an example for the case of high intensities (I>1015 W/cm2), the explosion of clusters under the action of very intense ultrashort laser fields is described.
Received: 26 November 1999 / Published online: 2 August 2000 相似文献
119.
ET da Costa CA Neves GM Hotta DT Vidal MF Barros AA Ayon CD Garcia CL do Lago 《Electrophoresis》2012,33(17):2650-2659
This paper describes a long-range remotely controlled CE system built on an all-terrain vehicle. A four-stroke engine and a set of 12-V batteries were used to provide power to a series of subsystems that include drivers, communication, computers, and a capillary electrophoresis module. This dedicated instrument allows air sampling using a polypropylene porous tube, coupled to a flow system that transports the sample to the inlet of a fused-silica capillary. A hybrid approach was used for the construction of the analytical subsystem combining a conventional fused-silica capillary (used for separation) and a laser machined microfluidic block, made of PMMA. A solid-state cooling approach was also integrated in the CE module to enable controlling the temperature and therefore increasing the useful range of the robot. Although ultimately intended for detection of chemical warfare agents, the proposed system was used to analyze a series of volatile organic acids. As such, the system allowed the separation and detection of formic, acetic, and propionic acids with signal-to-noise ratios of 414, 150, and 115, respectively, after sampling by only 30 s and performing an electrokinetic injection during 2.0 s at 1.0 kV. 相似文献
120.
Gregorio Snchez Francisco Ruiz Joaquín Garcia M. Ramírez Carmen de Arellano Gregorio Lpez 《Helvetica chimica acta》1997,80(8):2477-2485
The hydroxo complex (Bu4N)2[Ni2(C6F5)4(μ-OH)2]reacts with 2,3,4,5,6-pentafluoro benzenamine (C6F5-NH2), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC6H4, 4-MeOC6H4), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu4N)2[Ni2(C6F5)4(μ-C6F5NH)2] ( 1 ) and (Bu4N)2[{Ni(C6F5)2} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu4N[Ni(C6F5)2(ArN3Ar)] ( 3 – 5 ), Bu4N[Ni(C6F5)2(pyNPh)] ( 6 ), and Bu4N[Ni(C6F5)2(pyCONPh)] ( 7 ). The hydroxo.complex (Bu4N)2[{Ni(C6F5)2-(μ-OH)}2] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, 1H and 19F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu4N)2[{Ni(C6F5)2}2(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°. 相似文献