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61.
A theoretical study of homocyclic sulfur species S6, S7, and S8 was carried out using a molecular valence method involving stepwise approximations for orthogonality and core-valence interactions. The valence shell orbitals are described at the minimal basis level. The geometries of the molecules are predicted well as compared with other theoretical studies and the experimental values. The slight overestimation of the SS bond length is typical to the nonpolarized basis sets. The energies of the valence orbitals are well in accord with the conventional all-electron ab initio results. The trend in the stabilities of the three molecules is discussed. The present method provides an attractive possibility to study homocyclic and heterocyclic systems involving heavier chalcogens with no increase of the computing time.  相似文献   
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63.
The formation and crystal structures of bis(1‐naphthyl) diselenide ( 1 ) and bis{[2‐(N,N‐dimethylamino)methyl]phenyl} tetraselenide ( 2 ) are described. Whereas 1 can be produced in good yields, 2 is formed only as a minor product together with the known main product, bis{[2‐(N,N‐dimethylamino)methyl]phenyl} diselenide. The composition of the reaction mixture is semi‐quantitatively estimated by 77Se NMR spectroscopy and DFT calculations. The effect of the n2→σ*(Se–Se) and π→σ*(Se–Se) secondary bonding interactions on the Se–Se bonds is discussed both by DFT calculations and comparison with literature, as available. The bromination of 1 yields monomeric (1‐naphthyl)selenenyl bromide ( 3 ) in good yields. That of the reaction mixture of (C6H4CH2NMe2)Sex (x = 2–4) and Se8 afforded (C6H4CH2NMe2H)2[SeBr4] ( 4 ) and (C6H4CH2NMe2H)2[SeBr6] ( 5 ) in addition to (C6H4CH2NMe2)SeBr, which has been previously reported.  相似文献   
64.
We present rapid (<5 min) and efficient intact protein analysis by mass spectrometry (MS) using fully microfabricated and monolithically integrated capillary electrophoresis–electrospray ionization (CE–ESI) microchips. The microchips are fabricated fully of commercial inorganic–organic hybrid material, Ormocomp, by UV-embossing and adhesive Ormocomp–Ormocomp bonding (CE microchannels). A sheath-flow ESI interface is monolithically integrated with the UV-embossed separation channels by cutting a rectangular emitter tip in the end with a dicing saw. As a result, electrospray was produced from the corner of chip with good reproducibility between parallel tips (stability within 3.8–9.2% RSD). Thanks to its inherent biocompatibility and stable (negative) surface charge, Ormocomp microchips enable efficient intact protein analysis with up to ∼104 theoretical separation plates per meter without any chemical or physical surface modification before analysis. The same microchip setup is also feasible for rapid peptide sequencing and mass fingerprinting and shows excellent migration time repeatability from run to run for both peptides (5.6–5.9% RSD, n = 4) and intact proteins (1.3–7.5% RSD, n = 3). Thus, the Ormocomp microchips provide a versatile new tool for MS-based proteomics. Particularly, the feasibility of the Ormocomp chips for rapid analysis of intact proteins with such a simple setup is a valuable increment to the current technology.  相似文献   
65.
The feasibility of a microfluidic-based liquid chromatography-electrospray ionization/mass spectrometric system (HPLC-Chip/ESI/MS) was studied and compared to a conventional narrow-bore liquid chromatography-electrospray ionization/mass spectrometric (LC-ESI/MS) system for the analysis of steroids. The limits of detection (LODs) for oxime derivatized steroids, expressed as concentrations, were slightly higher with the HPLC-Chip/MS system (50–300 pM) using an injection volume of 0.5 μL than with the conventional LC-ESI/MS (10–150 pM) using an injection volume of 40 μL. However, when the LODs are expressed as injected amounts, the sensitivity of the HPLC-Chip/MS system was about 50 times higher than with the conventional LC-ESI/MS system. The results indicate that the use of HPLC-Chip/MS system is clearly advantageous only in the analysis of low-volume samples. Both methods showed good linearity and good quantitative and chromatographic repeatability. In addition to the instrument comparisons with oxime derivatized steroids, the feasibility of the HPLC-Chip/MS system in the analysis of non-derivatized and oxime derivatized steroids was compared. The HPLC-Chip/MS method developed for non-derivatized steroids was also applied to the quantitative analysis of 15 mouse plasma samples.  相似文献   
66.
We present the first monolithically integrated silicon/glass liquid chromatography-electrospray ionization microchip for mass spectrometry. The microchip is fabricated by bonding a silicon wafer, which has deep reactive ion etched micropillar-filled channels, together with a glass lid. Both the silicon channel and the glass lid have a through-wafer etched sharp tip that produces a stable electrospray. The microchip is also compatible with laser induced fluorescence (LIF) detection, due to the glass lid. Separation of drugs in less than 5 minutes using either SiO(2) (normal phase) or C(18) coated (reversed-phase) pillars with good sensitivity was demonstrated with mass spectrometric detection as well as separation of fluorescent compounds with LIF detection.  相似文献   
67.
68.
We show that on any compact Riemann surface with variable negative curvature there exists a measure which is invariant and ergodic under the geodesic flow and whose projection to the base manifold is 2-dimensional and singular with respect to the 2-dimensional Lebesgue measure.  相似文献   
69.
Orthogonality is a much desired property for MIMO coding. It enables symbol-wise decoding, where the errors in other symbol estimates do not affect the result, thus providing an optimality that is worth pursuing. It also paves the way for low complexity soft decision decoding, which for orthogonal complex MIMO codes is known for two transmit (Tx) antennas, i.e. for the Alamouti code. We propose novel soft decision decoders for the orthogonal complex MIMO codes on three and four Tx antennas and extend the old result of maximal ratio combining (MRC) to cover all orthogonal codes up to four Tx antennas.As a rule, a sophisticated transmission scheme encompasses forward error correction (FEC) coding, and its performance is measured at the FEC decoder instead of at the MIMO decoder. We introduce the receiver structure that delivers the MIMO decoder’s soft decisions to the demodulator, which in turn cranks out the logarithm of likelihood ratio (LLR) of each bit and delivers them to the FEC decoder. This significantly improves the receiver, where a maximum likelihood (ML) MIMO decoder makes hard decisions at a too early stage. Further, the additional gain is achieved with stunningly low complexity.  相似文献   
70.
When RhCl3 · 3H2O was treated with an excess of Te(CH2SiMe3)2, a mononuclear mer-[RhCl3{Te(CH2SiMe3)2}3] (1) was observed as the main product. By reducing the metal-to-ligand molar ratio, dinuclear [Rh2(μ-Cl)2Cl4{Te(CH2SiMe3)2}4] (2) was obtained in addition to 1. Further reduction of the metal-to-ligand ratio resulted in the formation of [Rh2(μ-Cl)2Cl4(OHCH2CH3){Te(CH2SiMe3)2}3] (3). The treatment of mer-[RhCl3(SMePh)3] (4) with two equivalents of Te(CH2SiMe3)2 affords a mixture of mer-[RhCl3{Te(CH2SiMe3)2}3] (1) and mer-[RhCl3{Te(CH2SiMe3)2}2(SMePh)] (5). All complexes 1-4 and 5 · ½EtOH were characterized by X-ray crystallography and 125Te NMR spectroscopy, where appropriate. The definite assignment of the 125Te chemical shifts enabled a plausible discussion of the assignment of some unknown resonances that were observed in the NMR spectra.  相似文献   
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