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31.
José Fernández Bertrán Boris La Serna Klaus Doerffel Klaus Dathe Gunther Kabish 《Journal of Molecular Structure》1982
The Fermi doublet V2?V3 + V4 of CH3CN in basic, inert and acidic solvents has been studied by IR and Raman spectroscopy. The values of W, the Fermi coupling coefficient, obtained from IR spectra varies with the nature of the solvent while W evaluated from Raman data remains constant at 12.5 ± 0.5 cm?1. The similar effects of Bronsted and Lewis acids on the band frequencies and intensities is evidence that the CN group complexes with acids via the N atom “n” electron pair and not the π bond. 相似文献
32.
Coldham I Crapnell KM Fernàndez JC Moseley JD Rabot R 《The Journal of organic chemistry》2002,67(17):6181-6187
A synthesis of the core ABC ring system of the manzamine alkaloids is described, starting from arecoline. The key steps involve a Claisen rearrangement to set up a 4-substituted-3-methylenepiperidine and a stereoselective azomethine ylide dipolar cycloaddition reaction. Condensation of the aldehyde 6 and sarcosine ethyl ester hydrochloride salt gives an intermediate azomethine ylide, which undergoes an intramolecular cycloaddition reaction to set up two new rings and three new chiral centers stereoselectively. The aldehyde 6 was not a suitable substrate for related azomethine ylide cycloaddition reactions with other amines. However, the related dimethyl acetal 26 could be condensed with a variety of amines to give the desired tricyclic products. The cycloaddition reaction with N-methyl or N-allyl glycine ethyl ester gave almost exclusively the exo adduct, whereas cycloaddition with glycine ethyl ester gave the endo adduct. 相似文献
33.
The solubilization of benzo[a]pyrene by organic solvents (dioxane, toluene and dichloromethane) and a surfactant (Triton X-100) was investigated. These media were successfully used for the determination of benzo[a]pyrene using fluorescence detection, with excellent limits of detection and large linear analytical ranges. Benzo[a]pyrene was detected in coal washing waters using liquid chromatography with fluorescence detection. The stability of this compound in dioxane was also examined. 相似文献
34.
Rodríguez JL Souto RM Fernández-Mérida L Pastor E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(9):2134-2142
Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state. 相似文献
35.
Reaction conditions and structure of the starting enamines (cyclic or open-chain) determine greatly the final products of the title reactions. Whereas in benzene and acetonitrile, DMAD and 1 give a mixture of the diastereoisomeric dienamines 5, in methanol they afford pirrolizine 3. Enaminofuranones 2 and 10 furnish the corresponding “Michael adducts” 7a,b,c and 11a,b,c but fail to yield pirrolizines. It has been demonstrated that above b and c adducts differ exclusively on the arrangement of groups around a chiral axis. 相似文献
36.
Angel Alberola Luis Calvo Teresa Rodríguez Rodríguez Carmen Saudo 《Journal of heterocyclic chemistry》1992,29(2):445-450
The reactivity of 3-methyl-5-phenylisoxazole against electrophilic compounds in the presence of different bases is studied. With n-BuLi, alkylated products at C-4 position and C-3 methyl group, and, in a few cases, dialkylated isoxazoles are obtained. When the reactions are carried out with LICA, the nature of the alkylated products depends on the alkyl halide used. By using LICA-TMEDA, as deprotonating system, regio-selective reaction at the C-3 methyl group is found. 相似文献
37.
Fernández-Sánchez C Tzanov T Gübitz GM Cavaco-Paulo A 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,58(2):149-156
Six different compounds capable of mediating laccase-catalysed reactions have been tested by cyclic voltammetry. They exhibited quasi-reversible electrodic behaviour with formal redox potentials ranging from 150 to 800 mV (E(0)' vs. SCE). The immersion of a laccase-coated glassy carbon electrode (GCE) in mediator solutions generated large cathodic catalytic currents easily recorded by cyclic voltammetry at low-potential scan rates. This current showed two well-defined pH profiles, which correlated with the variation of the mediator redox potentials at the pH range tested. The relevant effect of temperature on the activity of laccase has been assessed here. Likewise, it was shown that the current record varied with the substrate concentration. This trend fitted Michaelis-Menten kinetics, which allowed us to give an estimation of the affinity of the fungal laccase for the different mediators. 相似文献
38.
René Guardiola Romero Angel Dago Morales Julio Duque Rodríguez José Fernández Bertrán 《Transition Metal Chemistry》1992,17(6):573-574
The structure of K3(Me4N)3[Co(CN)6]2·3H2O has been determined from three-dimensional X-ray diffraction data. The unit cell is formed by parallel layers of cobalt
octahedra [CoC6] and potassium octahedra, [K(1)N5O(1)], separated byc/2. In each layer both types of octahedra are located alternatively. The [MeN4]+ tetrahedra are located in the cavities between the two layers of octahedra. The crystal structure of this compound is the
first example of its type.
TMC 2483 相似文献
39.
Concha-Graña E Turnes-Carou MI Muniategui-Lorenzo S López-Mahía P Fernández-Fernández E Prada-Rodríguez D 《Journal of chromatography. A》2004,1047(1):147-155
The scope of this work is the development of a rapid, reliable and sensitive method for the analysis of organochlorine pesticides from soils by pressurized liquid extraction (PLE). The effect of four parameters (temperature, pressure, static time and cell volume) on the extraction efficiency was studied. The great extracting power of the PLE causes the extraction of numerous interfering substances, so a more efficient purification of this extract was necessary. In this work several sorbents have also been assayed to carry out the purification of soil samples: Florisil, silica, alumina, carbon, as well as combinations of them. Finally, the proposed analytical method was validated using a certified reference soil material (CRM804-050) and the results were compared with those obtained by other extraction techniques (Soxhlet and microwave-assisted extraction). 相似文献
40.
Tomás Pérez-Ruiz Carmen Martínez-Lozano Virginia Tomás Antonio Sanz Jesús Martín 《Fresenius' Journal of Analytical Chemistry》1998,362(4):399-403
A flow-injection configuration is proposed for the fluorimetric determination of ethylenethiourea. The procedure is based
on the inhibitory effect of ethylenethiourea on the oxidation of thiamine to thiochrome by mercury(II). A linear calibration
graph was obtained between 0.1 and 2.0 μg mL–1, with a sampling rate of 40 samples per hour and a relative standard deviation of about 1.11%. The usefulness of the method
was tested for the determination of ethylenethiourea residues in water, milk, potatoes, pear, grape and apple.
Received: 26 January 1998 / Revised: 6 April 1998 / Accepted: 9 April 1998 相似文献