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161.
Ramachandra S Schuermann KC Edafe F Belser P Nijhuis CA Reus WF Whitesides GM De Cola L 《Inorganic chemistry》2011,50(5):1581-1591
Two luminescent ruthenium complexes containing tripod-type end groups linked through a rigid spacer to a phenanthroline derivative, able to confer an axial geometry to the complexes, are described. One of the compounds is functionalized with thioacetate groups in order to link the metal complex to metallic surfaces. The photophysical and electrochemical behavior of the complexes are studied in solution and on conductive substrates and, furthermore, self-assembled monolayers are investigated in a junction using gold and an indium gallium eutectic, as electrodes, and by time-resolved confocal microscopy. The results show that the complexes form very stable and well-ordered monolayers because of the tripod system, which can anchor the complex almost perpendicular to the surfaces. 相似文献
162.
A propeller-shaped boron-nitrogen compound (NB(3)) with three binding sites for fluoride anions was synthesized and investigated by optical absorption, luminescence, and ((1)H, (11)B, (13)C, (19)F) NMR spectroscopy. Binding of fluoride in dichloromethane solution occurs in three clearly identifiable steps and leads to stepwise blocking of the three initially present nitrogen-to-boron charge transfer pathways. As a consequence, the initially bright blue charge transfer emission is red-shifted and decreases in intensity, until it is quenched completely in presence of large fluoride excess. Fluoride binding constants were determined from global fits to optical absorption and luminescence titration data and were found to be K(a1) = 4 × 10(7) M(-1), K(a2) = 2.5 × 10(6) M(-1), and K(a3) = 3.2 × 10(4) M(-1) in room temperature dichloromethane solution. Complexation of fluoride to a given dimesitylboryl site increases the electron density at the central nitrogen atom of NB(3), and this leads to red shifts of the remaining nitrogen-to-boron charge transfer transitions involving yet unfluorinated dimesitylboryl groups. 相似文献
163.
Leonelli F Blesi F Dirito P Trombetta A Ceccacci F La Bella A Migneco LM Marini Bettolo R 《The Journal of organic chemistry》2011,76(16):6871-6876
The problem of constructing diastereoselectively the C/D ring system of stemarane diterpenes from a bicyclo[2.2.2]octane intermediate was solved resulting in very simple synthesis of (+)-13-stemarene 1. The obtaining of the latter represents also a formal synthesis of (+)-18-deoxystemarin 2. In the key step, the epimeric mixture 10, dissolved in toluene, was converted by the action of TsOH into (+)-stemar-13-en-15-one 28. 相似文献
164.
Reviriego F Navarro P Arán VJ Jimeno ML García-España E Latorre J Yunta MJ 《The Journal of organic chemistry》2011,76(20):8223-8231
By using an improved synthetic method reported earlier, the cyclic stannoxanes obtained from RN-diethanolamine (R = Me, Bu) and dibutyltin oxide have been reacted with 1H-pyrazole-3,5-dicarbonyl dichloride to afford 26-membered diaza tetraester crowns (1, R = Me; 3, R = Bu) and 39-membered triaza hexaester crowns (2, R = Me; 4, R = Bu). The new structures were identified from their analytical and spectroscopic ((1)H and (13)C NMR, FAB-MS, and/or ESI-MS) data. Both diaza tetraester crowns (1 and 3), containing two 1H-pyrazole units, self-assemble into dimeric species through the formation of four hydrogen bonds involving the two NH pyrazole groups and the two tertiary amine groups of both crowns, as proved by X-ray crystallography and NMR analysis. Preliminary NMR, ESI-MS, MALDI-TOF-MS, and molecular modeling studies suggest that, in CDCl(3) solution, 1 interacts with ethyleneurea (ETU), affording 1:1, 2:1, and 2:2 1-ETU complexes. 相似文献
165.
Fernández N Carrillo L Vicario JL Badía D Reyes E 《Chemical communications (Cambridge, England)》2011,47(45):12313-12315
We have developed a highly efficient procedure for carrying out the catalytic enantioselective (3+2) cycloaddition between enals and stable azomethine ylides such as isoquinolinium and phthalizinium methylides. Under the optimized reaction conditions highly substituted chiral pyrroloisoquinolines and pyrrolophthalazines have been obtained in high yields and excellent diastereo- and enantioselectivities. 相似文献
166.
167.
Thomas M. Krülle Oscar Barba Susan H. Davis Graham Dawson Martin J. Procter Thomas Staroske Gerard H. Thomas 《Tetrahedron letters》2007,48(9):1537-1540
A simple one-pot method for the synthesis of 6-fluoro- and 6,7-difluoro-1-naphthoic acid is described. 6-Fluoro-1-naphthoic acid can be converted into 7-fluoro-1-naphthoic acid in three straightforward steps. 相似文献
168.
The intramolecular electron transfer reaction within the binuclear complex formed between tetraamminepyrazinecarboxylatocobalt(III) and aquopentacyanoferrate(II) ions is studied in various binary aqueous media at different temperatures. Results could not be explained on the basis of a primitive model. Experimental data were fitted by using a multiparameter regression which shows the important role played by specific interactions on reactivity. © 1993 John Wiley & Sons, Inc. 相似文献
169.
Jos María Miguel del Corral Marina Gordaliza Jos-Luis Lpez Esther Del Olmo M. Angeles Castro M. Luisa Lpez 《Helvetica chimica acta》1995,78(7):1793-1796
The configuration of several keto-cyclolignans related to podophyllotoxin has been reviewed. Under basic catalysis, the configuration at the C-atom in α-position to the lactone carbonyl group in podophyllotoxone is inverted instead of the C-atom in α-position to the ketone group, as it has been reported. 相似文献
170.
The system Fe(II)-5-Aphen-H2O was studied. The spectroscopic and electrochemical results show that only one stable complex between Fe(II) and 5-Aphen forms, having a 1:3 stoichiometric ratio. The spectrophotometry study allowed determination of the formation constant of the complex (log β3 = 23.42 ± 0.06). Also, the stability of the complex was evaluated as a function of pH; it was found that it decomposed at low pH values depending on the concentration and a pseudo-first order kinetics constant associated with k′ = 0.011 min−1. The results are in agreement with the electrochemical behaviour observed in the system, which indicated that at pH 1.33 the destruction of the complex [Fe(5-Aphen)3]2+ took place as a function of time; however, when the experiments were carried out at pH 6.19 the complex was stable. The thermodynamic data obtained through the use of MEDUSA allowed construction of predominance zone diagrams of the system Fe(II)-5-Aphen-H2O under the experimental conditions used. The thermodynamic results represented in the PZD describe the experimental behaviour reported in this work. 相似文献