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101.
A combination of two-dimensional nuclear magnetic resonance (NMR) proton relaxometry and differential interference contrast
optical microscopy is used to compare the pore structures of hydroxyethyl methacrylate-based hydrogels used in conventional
contact lenses with three silicone hydrogels primarily developed for continuous-wear contact lenses. It is shown that both
types of hydrogel have a connected network of nanopores but that, in addition, the silicone hydrogels contain pores on the
micrometer scale that enhances their permeability. The potential of other two-dimensional NMR relaxation and diffusion methods
for detailed characterization of hydrogels is discussed. 相似文献
102.
The Baeyer-Villiger reactions of acetone and 3-pentanone, including their fluorinated and chlorinated derivatives, with performic acid have been studied by ab initio and DFT calculations. Results are compared with experimental findings for the Baeyer-Villiger oxidation of aliphatic fluoro and chloroketones. According to theoretical results, the first transition state is rate-determining for all substrates even in the presence of acid catalyst. Although the introduction of acid into the reaction pathway leads to a dramatic decrease in the activation energy for the first transition state (TS), once entropy is included in the calculations, the enthalpic gain is lost. Of all substrates examined, pentanone reacts with performic acid via the lowest energy transition state. The second transition state is also lowest for pentanone, illustrating the accelerating effect of the additional alkyl group. Interestingly, there is only a small energetic difference in the transition states leading to migration of the fluorinated substituent versus the alkyl substituent in fluoropentanone and fluoroacetone. These differences match remarkably well with the experimentally obtained ratios of oxidation at the fluorinated and nonfluorinated carbons in a series of aliphatic ketones (calculated, 0.3 kcal/mol, observed, 0.5 kcal/mol), which are reported herein. The migration of the chlorinated substituent is significantly more difficult than that of the alkyl, with a difference in the second transition state of approximately 2.6 kcal/mol. 相似文献
103.
104.
Prof. Francesca Caterina Izzo Matilde Kratter Dr. Austin Nevin Prof. Elisabetta Zendri 《ChemistryOpen》2021,10(9):904-921
Up to 70 % of the oil paintings conserved in collections present metal soaps, which result from the chemical reaction between metal ions present in the painted layers and free fatty acids from the lipidic binders. In recent decades, conservators and conservation scientists have been systematically identifying various and frequent conservation problems that can be linked to the formation of metal soaps. It is also increasingly recognized that metal soap formation may not compromise the integrity of paint so there is a need for careful assessment of the implications of metal soaps for conservation. This review aims to critically assess scientific literature related to commonly adopted analytical techniques for the analysis of metal soaps in oil paintings. A comparison of different analytical methods is provided, highlighting advantages associated with each, as well as limitations identified through the analysis of reference materials and applications to the analysis of samples from historical paintings. 相似文献
105.
106.
This review provides analysts with critical insights of current approaches for quantification by laser ablation-inductively coupled plasma-mass spectrometry in the field of elemental imaging. This encompasses both calibration strategies that have been used with success in imaging biological samples, as well as those with potential to improve analytical accuracy and precision if applied to imaging. Methods reviewed include the use of CRMs, laboratory prepared matrix matched standards, internal standardisation, online standard addition and a variety of novel approaches that makes elemental imaging accessible to a wider base of analysts. The importance of quantification and factors affecting its use in imaging will also be considered. 相似文献
107.
Solvent-free films of poly (ethylene oxide)–silver triflate (PEO–AgCF3SO3)/MgO-based nanocomposite polymer electrolytes (PEO)50AgCF3SO3–x wt.% MgO (x = 1, 3, 5, 7, and 10) obtained using solution casting technique were found to exhibit an appreciably good complexation of
MgO nanofiller within the polymer electrolyte system and non-Debye type of relaxation as revealed by Fourier transform infrared
and complex impedance analyses. Optimized filler (5 wt.% MgO) when incorporated into the polymer electrolyte resulted in a
maximum electrical conductivity of 2 × 10−6 S cm−1 in conjunction with a silver ionic transference number (t
Ag+) of 0.23 at room temperature (298 K). Detailed structural, thermal, and surface morphological investigation indicated a slight
reduction in the degree of crystallinity owing to the addition of MgO nanofiller. 相似文献
108.
109.
Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 ± 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments. 相似文献
110.
J. F. Donegan J. P. Doran R. P. Stanley J. Hegarty
R. D. Feldman
R. F. Austin 《Applied Surface Science》1991,50(1-4):321-324The technique of resonant Rayleigh scattering is used to determine the homogeneous linewidth across the inhomogeneously broadened exciton resonance in a Cd0.25Zn0.75Te/ZnTe multiple quantum well structure. An order of magnitude increase of the Rayleigh scattering signal over background is observed on tuning a narrow-band laser through the exciton resonance at low temperatures. Spectral and temporal measurements show the effect to be a true scattering process rather than luminescence. The interface and alloy fluctuations in the quantum well give rise to spatial fluctuations in the dielectric response of the system while the large exciton resonance causes strong enhancement of scattering. The homogeneous linewidth was calculated across the exciton resonance. The technique is compared with the dephasing and hole-burning techniques more commonly used in homogeneous linewidth measurements. 相似文献