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41.
Simultaneous enantioseparations of 15 racemic aromatic amino acids and L-mimosine for their chiral discrimination were achieved by neutral selector-modified capillary electrophoresis (CE) and by charged selector-modified CE. Among the diverse cyclodextrins (CDs) examined, hydroxypropyl (HP)-alpha-CD as the neutral selector and highly sulfated (HS)-gamma-CD as the charged selector provided best chiral environments of different enantioselectivities. Fairly good enantiomeric resolutions were achieved with the HP-alpha-CD mode except for racemic 6-hydroxy-3,4-dihydroxyphenylalanine, threo-3,4-dihydroxyphenylserine and homophenylalanine while high-resolution separations of all the enantiomeric pairs were achieved in the HS-gamma-CD mode except that L-mimosine was not detected and a partial resolution (0.6) for threo-3,4-dihydroxyphenylserine enantiomers. Relative migration times to that of internal standard under the respective optimum conditions were characteristic of each enantiomer with good precision (% RSD: 0.7-3.8), thereby enabling to cross-check the chemical identification of aromatic amino acids and also their chiralities. The method linearity was found to be adequate (r> 0.99) for the chiral assay of the aromatic amino acids investigated. When applied to extracts of three plant seeds, nonprotein amino acids such as L-mimosine (42 nug/g) from Mimosa pudica Linné, and L-3,4-dihydroxyphenylalanine (268 nug/g) from Vicia faba were positively detected along with L-tryptophan, L-phenylalanine and L-tyrosine. 相似文献
42.
Poly(vinyl chloride) (PVC)-based membrane of pentathia-15-crown-5 exhibits good potentiometric response for Hg2+ over a wide concentration range (2.51 × 10−5 to 1.00 × 10−1 mol dm−3) with a slope of 32.1 mV per decade of Hg2+ concentration. The response time of the sensor is as fast as 20 s. The electrode has been used for a period of six weeks and exhibits fairly good discriminating ability towards Hg2+ in comparison to alkali, alkaline and some heavy metal ions. The electrode can be used in the pH range from 2.7 to 5.0. 相似文献
43.
44.
《Electroanalysis》2003,15(4):287-293
Homooxacalix[3]arene derivatives are effective ionophores for constructing serotonin‐selective membrane electrodes. An electrode based on one of the derivatives, tris(methoxyphenylpropyloxy)hexahomooxacalix[3]arene‐triethyl ether, with potassium tetrakis(p‐chlorophenyl)borate (20 mol% relative to the ionophore) as an ionic additive and bis(2‐ethylhexyl) sebacate as a solvent mediator in a poly(vinyl chloride) membrane matrix, displayed much better selectivity for serotonin than for various organic ammonium ions and inorganic cations. The electrode exhibited a near‐Nernstian response to serotonin in the concentration range of 2×10?4 to 1×10?2 M with a slope of 56.4 mV per concentration decade in physiological saline containing 150 mM NaCl and 10 mM Na2HPO4/NaH2PO4 (pH 7.4). The limit of the detection was 8×10?5 M. The selectivity pattern of this electrode was quite different from that of an electrode using calix[6]arene‐hexaacetic acid hexaethyl ester, a well‐known ionophore for primary organic ammonium ions, which did not induce an enhanced response to serotonin. The developed electrode was used for the active loading of serotonin in liposomes induced by transmembrane pH gradients. 相似文献
45.
Tullio Caronna Bruno M. Vittimberga Matthew E. Kornn W. Grant McGimpsey 《Journal of photochemistry and photobiology. A, Chemistry》1995,90(2-3):137-140
The photochemistry of a variety of dicyanopyridines (2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dicyanopyridine) in solution at room temperature was investigated. Pulsed UV (308 nm) laser irradiation in deoxygenated acetonitrile yields the triplet state with lifetimes between 4 and 10 μs and absorption bands in the 400 and 320 nm regions. In the presence of added HCl an air-insensitive transient (τ ≈ 10–12 μs, λmax ≈ 360–380 nm) was observed, suggesting the formation of a protonated excited state.
Irradiation in the presence of amines resulted in the production of the pyridyl radical anion (τ ≈ 40–80 μs, air sensitive, λmax ≈ 360–380 nm) formed by electron transfer from the amine to the pyridine triplet excited state. Stern-Volmer analysis gave electron transfer rate constants in the range (1–8) × 10−8 M−1 s−1.
In methanol solvent, irradiation yielded an air-insensitive transient assigned as the neutral pyridyl radical (τ ≈ 30–200 μs, λmax ≈ 370–385 nm). The formation of these transients is discussed in the context of previous photochemical electron spin resonance and product studies. 相似文献
46.
The aim of this paper is to complement existing oscillation results for third-order neutral delay differential equations by establishing sufficient conditions for nonexistence of so-called Kneser solutions. Combining newly obtained results with existing ones, we attain oscillation of all solutions of the studied equations. 相似文献
47.
A. Kamitani T. Takayama A. Tanaka S. Ikuno 《Physica C: Superconductivity and its Applications》2010,470(20):1189-1192
The inductive method for measuring the critical current density jC in a high-temperature superconducting (HTS) thin film has been investigated numerically. In order to simulate the method, a non-axisymmetric numerical code has been developed for analyzing the time evolution of the shielding current density. In the code, the governing equation of the shielding current density is spatially discretized with the finite element method and the resulting first-order ordinary differential system is solved by using the 5th-order Runge–Kutta method with an adaptive step-size control algorithm. By using the code, the threshold current IT is evaluated for various positions of a coil. The results of computations show that, near a film edge, the accuracy of the estimating formula for jC is remarkably degraded. Moreover, even the proportional relationship between jC and IT will be lost there. Hence, the critical current density near a film edge cannot be estimated by using the inductive method. 相似文献
48.
Valeria van Axel Castelli Antonella Dalla Cort Luigi Mandolini Valentina Pinto David N. Reinhoudt Fabrizio Ribaudo 《Supramolecular chemistry》2013,25(2-3):211-219
The complexation of the salophen-uranyl metallocleft 2 and of its half-cleft analogue 3 with enones and other carbonyl compounds was assessed in chloroform by UV-Vis titration and, occasionally, by FT-IR measurements. Complexes with receptors 2 and 3 are in all cases more stable than those with the control unsubstituted uranyl-salophen 1 , showing that in addition to the primary binding force provided by coordination of the carbonyl oxygen to the uranium, a significant driving force for complexation, typically in the range of 2-3 kcal/mol, results from van der Waals interactions of the guest with the aromatic walls. Replacement of the phenyl group in 3 with larger aromatic residues to give 4 and 5 , led to enhanced complex stabilities, due to more extended contact surfaces between host and guest. 相似文献
49.
A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic-zero version of the continuous transformation of origin of current density (CTOCD-DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N-atoms in the inner rings was found to cause a planarity distortion in the studied N-doped systems. The geometric changes and charged nature of the studied N-doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties. 相似文献
50.
Coronary magnetic resonance angiography (MRA) acquired using steady-state free precession (SSFP) sequences tends to suffer from image artifacts caused by local magnetic field inhomogeneities. Flow- and gradient-switching-induced eddy currents are important sources of such phase errors, especially under off-resonant conditions. In this study, we propose to reduce these image artifacts by using a linear centric-encoding (LCE) scheme in the phase-encoding (PE) direction. Abrupt change in gradients, including magnitude and polarity between consecutive radiofrequency cycles, is minimized using the LCE scheme. Results from numeric simulations and phantom studies demonstrated that signal oscillation can be markedly reduced using LCE as compared to conventional alternating centric-encoding (ACE) scheme. The image quality of coronary arteries was improved at both 1.5 and 3.0 T using LCE compared to those acquired using ACE PE scheme (1.5 T: ACE/LCE=2.2+/-0.8/3.0+/-0.6, P=.02; 3.0 T: ACE/LCE=2.1+/-1.1/3.0+/-0.8, P=.01). In conclusion, flow- and eddy-currents-induced imaging artifacts in coronary MRA using SSFP sequence can be markedly reduced with LCE acquisition of PE lines. 相似文献