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61.
62.
[structure: see text]. A new strategy for the synthesis of substituted azulenes is reported, based on the reaction of beta'-bromo-alpha-diazo ketones with rhodium carboxylates. The key transformation involves intramolecular addition of a rhodium carbenoid to an arene pi-bond, electrocyclic ring opening, beta-elimination, tautomerization, and trapping to produce 1-hydroxyazulene derivatives. The synthetic utility of the method is enhanced by the ability of the triflate derivatives to participate in Suzuki coupling reactions, as illustrated in a synthesis of the antiulcer drug egualen sodium (KT1-32). 相似文献
63.
Anthony Deally James ClaffeyBrendan Gleeson Megan HoganHelge Müller-Bunz Siddappa PatilDonal F. O’Shea Matthias Tacke 《Polyhedron》2010
From the reaction of various 6-pyrrolylfulvenes (3a–3d) with Super Hydride (LiBEt3H), lithiated cyclopentadienide intermediates (4a–4d) were synthesised. These intermediates were then transmetallated with titanium tetrachloride TiCl4 to yield the pyrrolyl-substituted titanocenes bis-[((1-(4-methoxybenzyl)-pyrrole)2-)cyclopentadienyl]titanium(IV) dichloride (5a), bis-[((1-(4-methoxyphenyl)-pyrrole)2-)cyclopentadienyl]titanium(IV) dichloride (5b), bis-[((2,4-bis(4-methoxyphenyl)-1-methyl-pyrrole)2-)cyclopentadienyl]titanium(IV) dichloride (5c), bis-[((2-(4-methoxyphenyl)-1-methyl-pyrrole)2-)cyclopentadienyl]titanium(IV) dichloride (5d). Titanocene 5b crystallised and was characterised by X-ray crystallography. The four titanocenes 5a–5d were tested for their cytotoxicity through MTT-based in vitro tests on CAKI-1 cell lines in order to determine their IC50 values. Titanocenes 5a–5d were found to have IC50 values of 440 (±35), 68 (±14), 105 (±30), and 36 (±7) μM. 相似文献
64.
The detection of early-stage tumors in the breast by microwave imaging is challenged by both the moderate endogenous dielectric contrast between healthy and malignant glandular tissues and the spatial resolution available from illumination at microwave frequencies. The high endogenous dielectric contrast between adipose and fibroglandular tissue structures increases the difficulty of tumor detection due to the high dynamic range of the contrast function to be imaged and the low level of signal scattered from a tumor relative to the clutter scattered by normal tissue structures. Microwave inverse scattering techniques, used to estimate the complete spatial profile of the dielectric properties within the breast, have the potential to reconstruct both normal and cancerous tissue structures. However, the ill-posedness of the associated inverse problem often limits the frequency of microwave illumination to the UHF band within which early-stage cancers have sub-wavelength dimensions. In this computational study, we examine the reconstruction of small, compact tumors in three-dimensional numerical breast phantoms by a multiple-frequency inverse scattering solution. Computer models are also employed to investigate the use of exogenous contrast agents for enhancing tumor detection. Simulated array measurements are acquired before and after the introduction of the assumed contrast effects for two specific agents currently under consideration for breast imaging: microbubbles and carbon nanotubes. Differential images of the applied contrast demonstrate the potential of the approach for detecting the preferential uptake of contrast agents by malignant tissues. 相似文献
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66.
Optical-access networks have been developed to remove the access-network bandwidth bottleneck. However, the current solutions do not adequately address the network economics to provide a truly cost-effective solution. Long-reach optical-access networks introduce a cost-effective solution by connecting the customer directly to the core network, bypassing the metro network, and, hence, removing significant cost. This paper charts the design and development of a 1024-way-split 100-km 10-Gb/s symmetrical network, which experimentally proves the feasibility of long-reach optical-access networks for both the upstream and downstream transmission. 相似文献
67.
Jeremy Robertson Matthew J. Palframan Stephen A. Shea Kirill Tchabanenko William P. Unsworth Chase Winters 《Tetrahedron》2008,64(52):11896-11907
5-exo Cyclisation of vinyl-, aryl- and alkyl-radicals onto the aryl group of arylcarboxamides is followed by β-scission of the resulting spirocyclohexadienyl radicals with ejection of a carbamoyl radical. The fate of this radical depends on the substrate but, in the cases studied, either 5-endo cyclisation or direct reduction follows to give phthalimides, biaryls or β-arylethylamines. 相似文献
68.
Pressurized liquid extraction (PLE) and pressurized hot water extraction (PHWE) using a laboratory-made system are applied for the extraction of thermally labile components such as tanshinone I and IIA in Salvia miltiorrhiza. PLE and PHWE are carried out dynamically at a flow of 1 mL/min, temperature between 95-140 degrees C, applied pressure of 10-20 bars, and extraction times of 20 and 40 min, respectively. Effects of ethanol added into the water used in PHWE are explored. PLE is found to give comparable or higher extraction efficiencies compared with PHWE with reference to Soxhlet extraction for tanshinone I and IIA in Salvia miltiorrhiza. The tanshinone I and IIA present in the various medicinal plant extracts are determined by liquid chromatography and liquid chromatography-mass spectrometry. 相似文献
69.
Nonaqueous capillary electrophoresis (NACE) is a chemical separation technique that has grown in popularity over the past few years. In this report, we focus on the combination of heteroconjugation and deprotonation in the NACE separation of phenols using acetonitrile (ACN) as the buffer solvent. By preparing various dilute buffers consisting of carboxylic acids and tetrabutylammonium hydroxide in ACN, selectivity may be manipulated based on a solute's dissociation constant as well as its ability to form heterogeneous ions with the buffer components. ACN's low viscosity, coupled with its ability to allow for heteroconjugation, often leads to rapid and efficient separations that are not possible in aqueous media. In this report, equations are derived showing the dependence of mobility on various factors, including the pKa of the analyte, the pH and concentration of the buffer, and the analyte-buffer heteroconjugation constant (Kf). The validity of these equations is tested as several nitrophenols are separated at different pH values and concentrations. Using nonlinear regression, the Kf values for the heteroconjugate formation between the nitrophenols and several carboxylate anions are calculated. Also presented in this report are the NACE separations of the 19 chlorophenol congeners and the 11 priority pollutant phenols (used in US Environmental Protection Agency methods 604, 625/1625 and 8270B). 相似文献
70.