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131.
V. V. Bolotov V. E. Kan M. Yu. Biryukov E. V. Knyazev R. V. Shelyagin P. M. Korusenko S. N. Nesov Yu. A. Sten’kin 《Physics of the Solid State》2013,55(7):1459-1462
The origin of the low-frequency band (250–300 cm?1) in the Raman spectra of multi-walled carbon nanotubes (MWCNTs) produced by the CVD method has been studied. The studies performed by Raman spectroscopy, transmission electron microscopy, Auger spectroscopy, and X-ray photoelectron spectroscopy after chemical and thermal treatments allow the assumption that this band belongs to radial vibrations of carbon atoms in internal walls of MWCNTs. 相似文献
132.
Gøgsig TM Kleimark J Lill SO Korsager S Lindhardt AT Norrby PO Skrydstrup T 《Journal of the American Chemical Society》2012,134(1):443-452
A new efficient protocol for the nickel-catalyzed Heck reaction of aryl triflates with vinyl ethers is presented. Mild reaction conditions that equal those of the corresponding palladium-catalyzed Heck reaction are applied, representing a practical and more sustainable alternative to the conventional regioselective arylation of vinyl ethers. A catalytic system comprised of Ni(COD)(2) and 1,1'-bis(diphenylphosphino)ferrocene (DPPF) in combination with the tertiary amine Cy(2)NMe proved effective in the olefination of a wide range of aryl triflates. Both electron-deficient and electron-rich arenes proved compatible, and the corresponding aryl methyl ketone could be secured after hydrolysis in yields approaching quantitative. Good functional group tolerance was observed matching the characteristics of the analogous Pd-catalyzed Heck reaction. The high levels of catalytic activity were explained by the intermediacy of a cationic nickel(II) complex potentially responsible for the successive β-hydride elimination and base promoted catalyst regeneration. Although these elementary reactions are normally considered challenging, DFT calculations suggested this pathway to be favorable under the applied reaction conditions. 相似文献
133.
Chernov SV Dobrovolsky YA Istomin SY Antipov EV Grins J Svensson G Tarakina NV Abakumov AM Van Tendeloo G Eriksson SG Rahman SM 《Inorganic chemistry》2012,51(2):1094-1103
Three different perovskite-related phases were isolated in the SrGa(1-x)Sc(x)O(2.5) system: Sr(2)GaScO(5), Sr(10)Ga(6)Sc(4)O(25), and SrGa(0.75)Sc(0.25)O(2.5). Sr(2)GaScO(5) (x = 0.5) crystallizes in a brownmillerite-type structure [space group (S.G.) Icmm, a = 5.91048(5) ?, b = 15.1594(1) ?, and c = 5.70926(4) ?] with complete ordering of Sc(3+) and Ga(3+) over octahedral and tetrahedral positions, respectively. The crystal structure of Sr(10)Ga(6)Sc(4)O(25) (x = 0.4) was determined by the Monte Carlo method and refined using a combination of X-ray, neutron, and electron diffraction data [S.G. I4(1)/a, a = 17.517(1) ?, c = 32.830(3) ?]. It represents a novel type of ordering of the B cations and oxygen vacancies in perovskites. The crystal structure of Sr(10)Ga(6)Sc(4)O(25) can be described as a stacking of eight perovskite layers along the c axis ...[-(Sc/Ga)O(1.6)-SrO(0.8)-(Sc/Ga)O(1.8)-SrO(0.8)-](2).... Similar to Sr(2)GaScO(5), this structure features a complete ordering of the Sc(3+) and Ga(3+) cations over octahedral and tetrahedral positions, respectively, within each layer. A specific feature of the crystal structure of Sr(10)Ga(6)Sc(4)O(25) is that one-third of the tetrahedra have one vertex not connected with other Sc/Ga cations. Further partial replacement of Sc(3+) by Ga(3+) leads to the formation of the cubic perovskite phase SrGa(0.75)Sc(0.25)O(2.5) (x = 0.25) with a = 3.9817(4) ?. This compound incorporates water molecules in the structure forming SrGa(0.75)Sc(0.25)O(2.5)·xH(2)O hydrate, which exhibits a proton conductivity of ~2.0 × 10(-6) S/cm at 673 K. 相似文献
134.
Friedel-Crafts acylation has been known since the 1870s, and it is an important organic synthetic reaction leading to aromatic ketone products. Friedel-Crafts acylation is usually performed with carboxylic acid chlorides or anhydrides, while amides are generally not useful substrates in these reactions. Despite being the least reactive carboxylic acid derivative, we have found a series of amides capable of providing aromatic ketones in good yields (55-96%, 17 examples). We propose a mechanism involving diminished C-N resonance through superelectrophilic activation and subsequent cleavage to acyl cations. 相似文献
135.
Fragment-based drug discovery (FBDD) has become a new strategy for drug discovery where lead compounds are evolved from small molecules. These fragments form low affinity interactions (dissociation constant (K (D))?=?mM?-?μM) with protein targets, which require fragment screening methods of sufficient sensitivity. Weak affinity chromatography (WAC) is a promising new technology for fragment screening based on selective retention of fragments by a drug target. Kinases are a major pharmaceutical target, and FBDD has been successfully applied to several of these targets. In this work, we have demonstrated the potential to use WAC in combination with mass spectrometry (MS) detection for fragment screening of a kinase target-cyclin G-associated kinase (GAK). One hundred seventy fragments were selected for WAC screening by virtual screening of a commercial fragment library against the ATP-binding site of five different proteins. GAK protein was immobilized on a capillary HPLC column, and compound binding was characterized by frontal affinity chromatography. Compounds were screened in sets of 13 or 14, in combination with MS detection for enhanced throughput. Seventy-eight fragments (46?%) with K (D)?200?μM were detected, including a few highly efficient GAK binders (K (D) of 2?μM; ligand efficiency?=?0.51). Of special interest is that chiral screening by WAC may be possible, as two stereoisomeric fragments, which both contained one chiral center, demonstrated twin peaks. This ability, in combination with the robustness, sensitivity, and simplicity of WAC makes it a new method for fragment screening of considerable potential. 相似文献
136.
EK Raja SO Nilsson Lill DA Klumpp 《Chemical communications (Cambridge, England)》2012,48(65):8141-8143
Despite the relatively low reactivities of urea and thiourea functional groups towards nucleophilic attack, we have found conditions in which they are useful substrates in Friedel-Crafts reactions. The Br?nsted superacid, triflic acid, promotes these reactions and a mechanism is proposed involving dicationic, superelectrophilic intermediates. 相似文献
137.
V. V. Bolotov N. A. Davletkil’deev A. A. Korotenko E. Yu. Mosur O. Yu. Proskurina Yu. A. Sten’kin 《Technical Physics》2011,56(7):1053-1055
The hemoglobin adsorption in porous silicon is studied by the method of spectroscopic ellipsometry. The layer-by-layer component
distribution in the porous silicon-hemoglobin system shows that hemoglobin molecules penetrate through the porous layer with
a slight gradient of the protein volume fraction. 相似文献
138.
139.
Monson BB Lotto AJ Ternström S 《The Journal of the Acoustical Society of America》2011,129(4):2263-2268
The human voice spectrum above 5 kHz receives little attention. However, there are reasons to believe that this high-frequency energy (HFE) may play a role in perceived quality of voice in singing and speech. To fulfill this role, differences in HFE must first be detectable. To determine human ability to detect differences in HFE, the levels of the 8- and 16-kHz center-frequency octave bands were individually attenuated in sustained vowel sounds produced by singers and presented to listeners. Relatively small changes in HFE were in fact detectable, suggesting that this frequency range potentially contributes to the perception of especially the singing voice. Detection ability was greater in the 8-kHz octave than in the 16-kHz octave and varied with band energy level. 相似文献
140.
Naredla RR Zheng C Nilsson Lill SO Klumpp DA 《Journal of the American Chemical Society》2011,133(33):13169-13175
This Article presents the results from studies related to the chemistry of tricationic superelectrophiles. A series of triaryl methanols were ionized in Br?nsted superacids, and the corresponding tricationic intermediates were formed. The trications are found to participate in two types of reactions; both are characteristic of highly charged organic cations. One set of reactions occurs through charge migration. A second set of reactions occurs through deprotonation of an unusually acidic site on the tricationic species. One of the tricationic intermediates has been directly observed by low temperature NMR spectroscopy. These highly charged ions and their reactions have also been studied using density functional theory calculations. As a result of charge migration, electron density at a carbocation site is found to increase with progression from monocationic to pentacationic structures. 相似文献