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31.
Diego Mateo Andrea Santiago‐Portillo Josep Albero Sergio Navaln Mercedes Alvaro Hermenegildo García 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):18007-18012
Prolonged (weeks) UV/Vis irradiation under Ar of UiO‐66(Zr), UiO66 Zr‐NO2, MIL101 Fe, MIL125 Ti‐NH2, MIL101 Cr and MIL101 Cr(Pt) shows that these MOFs undergo photodecarboxylation of benzenedicarboxylate (BDC) linker in a significant percentage depending on the structure and composition of the material. Routine characterization techniques such as XRD, UV/Vis spectroscopy and TGA fail to detect changes in the material, although porosity and surface area change upon irradiation of powders. In contrast to BCD‐containing MOFs, zeolitic imidazolate ZIF‐8 does not evolve CO2 or any other gas upon irradiation. 相似文献
32.
Control of four-wave mixing phase-matching condition using the Brillouin slow-light effect in fibers
All-optical control of the phase-matching condition in four-wave mixing (FWM) processes is demonstrated using the Brillouin slow-light effect in optical fibers. A counterpropagating stimulated Brillouin scattering (SBS) pump has been used to control the phase velocity of the FWM pump in a wavelength conversion scheme. Both experimental results and theoretical simulations show an SBS-controlled 20 dB difference on the wavelength conversion efficiency. 相似文献
33.
Alajarín M Pastor A Orenes RA Goeta AE Steed JW 《Chemical communications (Cambridge, England)》2008,(34):3992-3994
The self-assembly of chiral tris(m-ureidobenzyl)amines to give dimeric capsules is a highly diastereoselective process in solution, while in the solid state, the formation of the corresponding capsules is not only diastereoselective but also regioselective. 相似文献
34.
35.
Mateo del Rio Dr. Carlos Palomino Cabello Veronica Gonzalez Dr. Fernando Maya Dr. Jose B. Parra Dr. Victor Cerdà Dr. Gemma Turnes Palomino 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11770-11777
Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L?1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings. 相似文献
36.
Alajarín M Cabrera J Pastor A Sanchez-Andrada P Bautista D 《The Journal of organic chemistry》2006,71(14):5328-5339
The reaction of 2-(phenylamino)- and 2-(dimethylamino)thiazoles with dimethyl acetylenedicarboxylate led unexpectedly to dimethyl 6-(phenylamino)- and 6-(dimethylamino)-3,4-pyridinedicarboxylates. Those compounds reasonably result from a sequence of reactions initiated by a [2 + 2] cycloaddition of the alkyne to the formal C=C of the thiazole ring. These pyridines were obtained in nearly all the cases assayed as the exclusive reaction products under rather mild conditions and in fair to good yields. In contrast, the regioisomeric 2-amino-3,4-pyridinedicarboxylates, which would result from a [4 + 2] cycloaddition followed by sulfur extrusion, were only obtained in one particular case. The two reaction paths leading alternatively to both regioisomers were investigated computationally. The respective [2 + 2] and [4 + 2] cycloadducts were found to be formed stepwise from a common dipolar intermediate. Notably, the step following the [2 + 2] cycloaddition (i.e., the ring opening of the fused cyclobutene intermediate to give an all-cis 1,3-thiazepine) was found to take place in a disrotatory mode. Although geometric constraints and electronic factors may reduce the energy for the disrotation, the implication of the fused five-membered ring in the electronic reorganization leading to the 1,3-thiazepine is determinant. In this sense, this step could be regarded also as a thermally allowed six-electron five-center disrotatory electrocyclic ring opening. The proposed mechanism was experimentally supported by the isolation of several intermediates and other experimental facts. 相似文献
37.
Marta Navarro Dr. Álvaro Mayoral Dr. Ester Mateo Dr. Ruth Lahoz Prof. Dr. Germán F. de la Fuente Prof. Dr. Joaquín Coronas 《Chemphyschem》2012,13(3):736-740
Precursor solutions for the synthesis of zeolites are irradiated by means of a Nd‐YAG laser. These solutions are subsequently submitted to a hydrothermal treatment and the results analyzed by X‐ray diffraction and electron microscopy. Laser irradiation promotes the formation of silica nanoparticles that nucleate into zeolite (silicalite‐1), following a hydrothermal treatment. The average crystal size (in the 0.6–3.6 μm range) of the zeolite exponentially decreases as a function of laser irradiation time. In addition, a longer irradiation time results in a narrower crystal size distribution. 相似文献
38.
Dr. Ilaria Gamba Iria Salvadó Gustavo Rama Miriam Bertazzon Mateo I. Sánchez Prof. Víctor M. Sánchez‐Pedregal Prof. José Martínez‐Costas Rosa F. Brissos Prof. Patrick Gamez Prof. José L. Mascareñas Prof. Miguel Vázquez López Prof. M. Eugenio Vázquez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13369-13375
A new bipyridine building block has been used for the solid‐phase synthesis of dinuclear DNA‐binding ruthenium(II) metallopeptides. Detailed spectroscopic studies suggest that these compounds bind to the DNA by insertion into the DNA minor groove. Moreover, the potential of the solid‐phase peptide synthesis approach is demonstrated by the straightforward synthesis of an octaarginine derivative that shows effective cellular internalization and cytotoxicity linked with strong DNA interaction, as evidenced by steady‐state fluorescence spectroscopy and AFM studies. 相似文献
39.
Prof. Dr. Mateo Alajarin Dr. Raul‐Angel Orenes Prof. Dr. Judith A. K. Howard Dr. Elinor C. Spencer Prof. Dr. Jonathan W. Steed Dr. Aurelia Pastor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2389-2397
Tris(2‐ and 3‐ureidobenzyl)amines with Cs symmetry self‐assemble in solution forming mixtures of regioisomeric capsular aggregates, one of which is chiral and the other centrosymmetric. Under certain conditions, a predominance of the centrosymmetric regioisomer is found before equilibrium, that is, a mixture close to the statistical ratio of the two species is reached. In the solid state, there is a preference for the centrosymmetric capsules. Molecular models of both regioisomeric aggregates have been built and analyzed for comparison. Guests inside capsules formed by self‐assembly of desymmetrized tris(3‐ureidobenzyl)amines feel different magnetic environments, depending on whether they are inside a chiral or an achiral regioisomeric container. Of special significance are the experiments with a more flexible triurea endowed with an ureidopropylic arm, which self‐assembles with the same efficiency as the more rigid tris(ureidobenzyl)amines. 相似文献
40.
The kinetics and mechanism of the reaction of complexation of chromium(III) with 2-acetyl-cyclohexanone has been investigated spectrophotometrically in aqueous solution at 50°C and ionic strength 0.5 mol dm?3 NaClO4. The equilibrium constants of the complex have been determined. The mechanism proposed to account for the kinetic data involves a double reversible pathway where both Cr3+ and Cr(OH)2+ react with the enol tautomer of the ligand with rate constants of 9.6 × 10?3 dm3 mol?1 s?1, and 3.69 × 10?2 dm3 mol?1 s?1, respectively. Some discussions are made on the basis of Eigen-Wilkins theory considering the effect of solvent exchange on the complex formation. 相似文献