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71.
The a.c. impedance of Pt∣NaCl∣Pt and C∣NaCl∣C cells was measured in the frequency range from 10?3 to 103 Hz. Two contributions to the interface impedance could be distinguished, hindered charge transfer and an adsorption/desorption or slow reaction contribution, the latter being the rate determining step in the frequency range studied. An approximately symmetric nonlinear dependence of both the capacitance and the conductance on overvoltage was found at the lowest frequencies, indicating that the crystal/electrode interface is in a state which can be characterized as close to equilibrium. It should be ensured by two electrochemical reactions of approximately equal rates. The concept of a temporarily reversible electrode is introduced. It is a result of the ability of ions to discharge at the interface and to produce a finite reservoir of adsorbed or absorbed reaction products. An external voltage increases or reduces this reservoir, and therefore only a transient electric current may be carried by a backward reaction. 相似文献
72.
States with private correlations but little or no distillable entanglement were recently reported. Here, we consider the secure distribution of such states, i.e., the situation when an adversary gives two parties such states and they have to verify privacy. We present a protocol which enables the parties to extract from such untrusted states an arbitrarily long and secure key, even though the amount of distillable entanglement of the untrusted states can be arbitrarily small. 相似文献
73.
The air stable asarone-derived Ru carbene 16, a robust olefin metathesis catalyst, can be easily separated after reaction by deposition on silica gel and reused up to nine times. This procedure provides products of excellent purity with low Ru content. 相似文献
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76.
Jackowski K Jaszuński M Kamieński B Wilczek M 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2008,193(1):147-149
We present new gas-phase NMR spectra which relate the resonance frequency of (3)He nucleus to the resonance frequency of the proton in tetramethylsilane (TMS). We discuss the dependence of (3)He resonance frequency on the density of the solvent gas, and we consider in detail the absolute shielding scales of both nuclei. Finally, we analyse the accuracy of the results, using the relationship between the resonance frequencies, absolute shielding constants and magnetic dipole moments of (1)H and (3)He nuclei. 相似文献
77.
Marco Carini Mauro Marongiu Karol Strutyski Akinori Saeki Manuel Melle‐Franco Aurelio Mateo‐Alonso 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(44):15935-15939
Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties. 相似文献
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Karol Kraszewski Ireneusz Tomczyk Dr. Aneta Drabinska Dr. Krzysztof Bienkowski Dr. Renata Solarska Dr. Marcin Kalek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11584-11592
The oxidative dearomatization of phenols with the addition of nucleophiles to the aromatic ring induced by hypervalent iodine(III) reagents and catalysts has emerged as a highly useful synthetic approach. However, experimental mechanistic studies of this important process have been extremely scarce. In this report, we describe systematic investigations of the dearomatizing hydroxylation of phenols using an array of experimental techniques. Kinetics, EPR spectroscopy, and reactions with radical probes demonstrate that the transformation proceeds by a radical-chain mechanism, with a phenoxyl radical being the key chain-carrying intermediate. Moreover, UV and NMR spectroscopy, high-resolution mass spectrometry, and cyclic voltammetry show that before reacting with the phenoxyl radical, the water molecule becomes activated by the interaction with the iodine(III) center, causing the Umpolung of this formally nucleophilic substrate. The radical-chain mechanism allows the rationalization of all existing observations regarding the iodine(III)-promoted oxidative dearomatization of phenols. 相似文献
80.
Michał Dąbrowski Dr. Przemysław Wyrębek Dr. Damian Trzybiński Prof. Krzysztof Woźniak Prof. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3782-3794
Robust, selective, and stable in the presence of ethylene, ruthenium olefin metathesis pre-catalyst, {[3-benzyl-1-(10-phenyl-9-phenanthryl)]-2-imidazolidinylidene}dichloro(o-isopropoxyphenylmethylene)ruthenium(II), Ru-3 , bearing an unsymetrical N-heterocyclic carbene (uNHC) ligand, has been synthesized. The initiation rate of Ru-3 was examined by ring-closing metathesis and cross-metathesis reactions with a broad spectrum of olefins, showing an unprecendented selectivity. It was also tested in industrially relevant ethenolysis reactions of olefinic substrates from renewable feedstock with very good yields and selectivities. 相似文献