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831.
Ma Q Chakraborty D Faglioni F Muller RP Goddard WA Harris T Campbell C Tang Y 《The journal of physical chemistry. A》2006,110(6):2246-2252
The current work utilizes the ab initio density functional theory (DFT) to develop a molecular level of the mechanistic understanding on the phenol alkylation in the presence of a cation-exchange resin catalyst, Amberlyst-15. The catalyst is modeled with the benzene sulfonic acid, and the effect of this acid on olefins such as isopropene (i-Pr) and tributene (t-Bu) in a phenol solution mimics the experimental condition. A neutral-pathway mechanism is established to account for early-stage high concentration of the phenolic ether observed in experiments. The mechanism involves an exothermic reaction between olefin and the benzene sulfonic acid to form ester followed by three reaction pathways leading to direct O-alkylation, o-C-alkylation, and p-C-alkylation. Our calculations conclude that O-alkylation to form the phenolic ether is the most energetically favorable in the neutral condition. An ionic rearrangement mechanism describes intramolecular migrations of the alkyl group from the phenolic ether to form C-alkylphenols, while the positively charged protonation significantly lowers transition barriers for these migrations. The ionic rearrangement mechanism accounts for high yields of o-C-alkylphenol and p-C-alkylphenol. Competition between the H atom and the alkyl R group at the substitutive site of the protonated ortho configuration is found to be the determining factor to the ortho/para ratio of C-alkylation products. 相似文献
832.
Erik M. Muller John Smedley Jen Bohon Xi Yang Mengjia Gaowei John Skinner Gianluigi De Geronimo Michael Sullivan Marc Allaire Jeffrey W. Keister Lonny Berman Annie Héroux 《Journal of synchrotron radiation》2012,19(3):381-387
Two transmission‐mode diamond X‐ray beam position monitors installed at National Synchrotron Light Source (NSLS) beamline X25 are described. Each diamond beam position monitor is constructed around two horizontally tiled electronic‐grade (p.p.b. nitrogen impurity) single‐crystal (001) CVD synthetic diamonds. The position, angle and flux of the white X‐ray beam can be monitored in real time with a position resolution of 500 nm in the horizontal direction and 100 nm in the vertical direction for a 3 mm × 1 mm beam. The first diamond beam position monitor has been in operation in the white beam for more than one year without any observable degradation in performance. The installation of a second, more compact, diamond beam position monitor followed about six months later, adding the ability to measure the angular trajectory of the photon beam. 相似文献
833.
834.
The deformation in uniaxial elongational flow of dispersed droplets in immiscible molten polymer blends was studied for negligible interfacial tension and for viscosity ratio p = η(drop)/η(matrix) between 0.005 and 13, with an original method based on quenching elongated specimens. Although drop deformation (drop major axis over initial diameter) was in the range 1 < λd < 5, a good overall agreement was found with the small deformation Newtonian theory, which predicts that the drop versus matrix deformation ranges from 5/3 to 0 when p increases from 0 to infinity. The theoretical prediction that for p lower than 1, the droplet should deform more than the faraway surrounding matrix, with a limiting ratio of 5/3 at vanishing droplet viscosity, was experimentally verified. 相似文献
835.
Lithiated diethyl prop-2-enylphosphonate adds to an aliphatic or an aromatic aldehyde, yielding a diastereomeric mixture of the kinetically controlled α-adduct. Upon warming, these adducts decompose back to starting materials to give finally the thermodynamically controlled γ-adducts, or undergo fragmentation to diethyl phosphate and (E) dienes. The distribution of the first product between these two pathways is a function of the aldehyde (aromatic vs. aliphatic) and of steric interactions operating within the two diastereomers of the adduct. 相似文献
836.
Valentyn Pozhydaiev Cyprien Muller Prof. Joseph Moran Dr. David Lebœuf 《Angewandte Chemie (International ed. in English)》2023,62(41):e202309289
β-(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum of biological properties, making them prime candidates for drug discovery. Conventional methods for their preparation often require engineered substrates that limit the flexibility of the synthetic routes and the diversity of compounds that can be accessed. Consequently, methods that provide rapid and versatile access to those scaffolds remain limited. To overcome these challenges, synthetic chemists have designed innovative and modular strategies to access the β-(hetero)arylethylamine motif, paving the way for their more extensive use in future pharmaceuticals. This review outlines recent progresses in the synthesis of (hetero)arylethylamines and emphasizes how these innovations have enabled new levels of molecular complexity, selectivity, and practicality. 相似文献