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181.
Imidazolium-based polymer supported gadolinium triflate as a heterogeneous recyclable Lewis acid catalyst for Michael additions 总被引:1,自引:0,他引:1
A heterogeneous Lewis acid catalytic system has been developed by incorporating gadolinium triflate on to poly[styrene-co-(1-((4-vinylphenyl)methyl)-3-methylimidazolium) tetrafluoroborate] (1-Gd(OTf)3), and the catalytic activity of this system has been examined for Michael additions of amines and thiols to α,β-unsaturated esters and acrylonitrile. The reactions proceed in moderate to excellent yields in the presence of catalytic system 1-Gd(OTf)3. The catalytic system could be efficiently recycled and reused. 相似文献
182.
183.
Zhipeng Xiang Wenjin Li Kai Wan Zhiyong Fu Zhenxing Liang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(2):e202214601
Molecule aggregation in solution is acknowledged to be universal and can regulate the molecule's physiochemical properties, which however has been rarely investigated in electrochemistry. Herein, an electrochemical method is developed to quantitatively study the aggregation behavior of the target molecule methyl viologen dichloride. It is found that the oxidation state dicationic ions stay discrete, while the singly-reduced state monoradicals yield a concentration-dependent aggregation behavior. As a result, the molecule's energy level and its redox potential can be effectively regulated. This work does not only provide a method to investigate the molecular aggregation, but also demonstrates the feasibility to tune redox flow battery's performance by regulating the aggregation behavior. 相似文献
184.
Dr. Andreas Eitzinger Justus Reitz Patrick W. Antoni Prof. Dr. Herbert Mayr Dr. Armin R. Ofial Jun.-Prof. Max M. Hansmann 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309790
A series of mesoionic, 1,2,3-triazole-derived N-heterocyclic olefins (mNHOs), which have an extraordinarily electron-rich exocyclic CC-double bond, was synthesized and spectroscopically characterized, in selected cases by X-ray crystallography. The kinetics of their reactions with arylidene malonates, ArCH=C(CO2Et)2, which gave zwitterionic adducts, were investigated photometrically in THF at 20 °C. The resulting second-order rate constants k2(20 °C) correlate linearly with the reported electrophilicity parameters E of the arylidene malonates (reference electrophiles), thus providing the nucleophile-specific N and sN parameters of the mNHOs according to the correlation lg k2(20 °C)=sN(N+E). With 21<N<32, the mNHOs are much stronger nucleophiles than conventional NHOs. Some mNHOs even excel the reactivity of mono- and diacceptor-substituted carbanions. It is exemplarily shown that the reactivity parameters thus obtained allow to calculate the rate constants for mNHO reactions with further Michael acceptors and predict the scope of reactions with other electrophilic reaction partners including carbon dioxide, which gives zwitterionic mNHO-carboxylates. The nucleophilicity parameters N correlate linearly with a linear combination of the quantum-chemically calculated methyl cation affinities and buried volumes of mNHOs, which offers a valuable tool to tailor the reactivities of strong carbon nucleophiles. 相似文献
185.
We prepared reversible micelles with dye loaded on the shells or cores by ion exchange. A poly(4-styrylmethyl triphenylphosphonium
chloride)-block-polystyrene diblock copolymer prepared from poly(4-vinylbenzylchloride)-block-polystyrene and triphenylphosphine
was reacted with methyl orange in a mixed solvent of benzene and acetonitrile to produce poly[4-styrylmethyl triphenylphosphonium
4-(4-dimethylamino)phenylazobenzenesulfonate]-block-polystyrene. The loading of the methyl orange on the micellar shells or
cores was dependent on the composition of the mixed solvents. Dynamic light scattering demonstrated that the loading of the
dye on the cores significantly expanded the micelles when compared to that on the shells. The loading of the dye on the cores
shifted the UV wavelength of the methyl orange, whereas that on the shells produced no changes in the UV wavelength. Transmission
electron microscopy confirmed the formation of the spherical micelles. 相似文献
186.
A series of sodium, potassium, rubidium, and cesium complexes of methyl tetrazolate was prepared and structurally characterized. Treatment of methyl tetrazole (MetetzH) with the group 1 hydroxides in water at ambient temperature afforded Na(Metetz)(H2O)2 (92%), K(Metetz) (92%), Rb(Metetz) (97%), and Cs(Metetz) (97%) as colorless solids after workup. These complexes were characterized by spectral and analytical methods, thermogravimetric analysis, and by X-ray crystallography. Na(Metetz)(H2O)2 adopts a structure that consists of approximately octahedrally coordinated sodium ions that form infinite chains built up by two μ2-aqua ligands and two μ2-N1,N2-tetrazolate ligands between each sodium atom. The aqua ligand hydrogen atoms engage in hydrogen bonding with uncoordinated nitrogen atoms to hold the chains together. K(Metetz) and Rb(Metetz) are isostructural, with eight-coordinate metal ions and two metal–nitrogen bonds per nitrogen atom in each Metetz ligand. Cs(Metetz) has 10-coordinate cesium ions with two cesium–nitrogen bonds to two of the Metetz ligand nitrogen atoms and three cesium–nitrogen bonds to the other two nitrogen atoms. K(Metetz), Rb(Metetz), and Cs(Metetz) exhibit new coordination modes for the tetrazolate ligand. 相似文献
187.
Laura M. Sprunger Amy Proctor William E. Acree Jr. Michael H. Abraham Nora Benjelloun-Dakhama 《Fluid Phase Equilibria》2008,270(1-2):30-44
Experimental partition coefficient data have been compiled from the published literature for the water/methyl acetate, water/ethyl acetate and water/butyl acetate partition systems, log P data, and for the gas/methyl acetate, gas/ethyl acetate and gas/butyl acetate partition systems, log K data. Application of the Abraham solvation parameter model to the sets of partition coefficients leads to equations that correlate the log P data and log K data to 0.18 log units for the three dry alkyl acetate solvents. Slightly larger deviations were noted for solute partition into both wet ethyl acetate and wet butyl acetate. The derived correlations were validated using training set and test set analyses. 相似文献
188.
This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L−1 Britton-Robinson buffer (pH 10) in 0.25 mol L−1 NaNO3. The homogenized mixture is injected at a flow rate of 10 μL s−1 toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from −0.3 to −1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV. The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mg L−1, with detection and quantification limits of 2 and 7 μg L−1, respectively. The sampling throughput is 25 h−1 if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h−1 if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. 相似文献
189.
The objective of this research was to use combustion synthesis to create a nano‐sized ZnO photocatalyst using citric acid as the fuel and zinc nitrate as the oxidant. The starting materials were mixed in a stoichiometric ratio, and a slurry precursor with high homogeneity was formed. The precursor was ignited at room temperature, resulting in dry, loose, and voluminous ZnO powders. The powders, characterized by SEM, TEM and XRD, showed a particle size range of 40 to 80 nm with a wurtzite structure. The ZnO powders were introduced as a photocatalyst for the degradation of methyl orange, which was adopted as a model compound. UV light (6W) was used as the irradiation source to induce synthesized ZnO powders to perform catalytic activity. The photocatalytic reaction was executed in 40 mL of a 10 ppm methyl orange aqueous solution under 254 nm UV illumination. In this work, it was observed that both UV light and ZnO powders are needed for the photocatalytic reaction. In addition, it was found that increasing the amount of ZnO powder present in the MO (methyl orange‐C14H14N3NaO3S) solution did not correlate directly with an increase in photocatalytic ability. It was found that the scattering problem of UV light also needs to be considered. The optimized photocatalytic degradation ratio in this work reached 92.7%. 相似文献
190.
Triphenylmethane (TPM) was used as the initiator-transfer-terminator agent (iniferter) for the pseudo-living radical polymerization of methyl methacrylate (MMA) in cyclohexanone (CHO) for the first time. The pseudo-living radical polymerization of styrene is also investigated for comparison. The polymerizations both exhibit a linear increase of number molecular weight (Mn) with conversion and the obtained polymer can be utilized as a macroinitiator for the successful chain extension. Other factors such as polymerization temperature and the molar ratio of monomer-to-iniferter were investigated and the polymerization results also showed pseudo-living characteristics. Furthermore, other triarylmethanes with substituents, such as tris-(p-acetylphenyl) methane (TAcPM) and tris-(p-carboxyphenyl) methane (TCOPM), were also employed. The results further confirmed that the other compounds with similar structure can also be used as the iniferter. 相似文献