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111.
Cyclodextrin-modified electrokinetic chromatography (CD-EKC) was investigated for the separation of 12 monomethylbenz[a]anthracene (MBA) isomers. Combined use of a polymeric surfactant, poly(sodium 10-undecenyl sulfate) (poly-SUS), with various types of neutral cyclodextrins (CDs) [beta-CD, gamma-CD, dimethyl-beta-CD (DM-beta-CD), trimethyl-beta-CD (TM-beta-CD) and hydroxypropyl-beta-CD (HP-beta-CD)] were successful in CD-EKC separation of the MBA isomers. Baseline resolution of 10 of the 12 isomers, except for 9-MBA and 2-MBA, was achieved with gamma-CD at pH 9.75. The beta-CD, gamma-CD, and beta-CD derivatives (DM-beta-CD, TM-beta-CD, HP-beta-CD) were found to have different resolution and selectivity. Additionally, the tR/t0 values of isomers were found to be dependent on the type and concentration of the CD additives. In general, tR/t0 values of MBA isomers decrease with an increase in the concentration of beta-CD derivatives, whereas the reversed was true when the concentrations of native beta-CD and gamma-CD were varied. The combination of 5 mM gamma-CD, 0.5% (w/v) poly-SUS, 35% (v/v) acetonitrile at a pH of 9.75 provided the best selectivity and resolution of the MBA isomers with a separation time of 110 min. However, the use of 30 mM DM-beta-CD under similar EKC conditions resulted in much faster separation (ca. 16 min) of 10 MBA isomers. 相似文献
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In this study, the association behavior of pyrene with different dissolved humic materials (DHM) was investigated utilizing
the recently developed segmented frequency-domain fluorescence lifetime method. The humic materials involved in this study
consisted of three commercially available International Humic Substances Society standards (Suwannee River fulvic acid reference,
SRFAR, Leonardite humic acid standard, LHAS, and Florida peat humic acid standard, FPHAS), the peat derived Amherst humic
acid (AHA), and a chemically bleached Amherst humic acid (BAHA). It was found that the three commercial humic materials displayed
three lifetime components, while both Amherst samples displayed only two lifetime components. In addition, it was found that
the chemical bleaching procedure preferentially removed red wavelength emitting fluorophores from AHA. In regards to pyrene
association with the DHM, different behavior was found for all commercially available humics, while AHA and BAHA, which displayed
strikingly similar behavior in terms of fluorescence lifetimes. It was also found that there was an enhancement of pyrene’s
measured lifetime (combined with a decrease in pyrene emission) in the presence of FPHAS. The implications of this long lifetime
are discussed in terms of (1) quenching mechanism and (2) use of the fluorescence quenching method used to determine the binding
of compounds to DHM.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
114.
Paula Berton Noureen Siraj Susmita Das Sergio de Rooy Rodolfo G. Wuilloud Isiah M. Warner 《Molecules (Basel, Switzerland)》2021,26(1)
In this study, three magnetic ionic liquids (MILs) were investigated for extraction of four estrogens, i.e., estrone (E1), estradiol (E2), estriol (E3), and ethinylestradiol (EE2), from environmental water. The cation trihexyl(tetradecyl)phosphonium ([P66614]+), selected to confer hydrophobicity to the resulting MIL, was combined with tetrachloroferrate(III), ferricyanide, and dysprosium thiocyanate to yield ([P66614][FeCl4]), ([P66614]3[Fe(CN)6]), and ([P66614]5[Dy(SCN)8]), respectively. After evaluation of various strategies to develop a liquid–liquid microextraction technique based on synthesized MILs, we placed the MILs onto a magnetic stir bar and used them as extracting solvents. After extraction, the MIL-enriched phase was dissolved in methanol and injected into an HPLC–UV for qualitative and quantitative analysis. An experimental design was used to simultaneously evaluate the effect of select variables and optimization of extraction conditions to maximize the recovery of the analytes. Under optimum conditions, limits of detection were in the range of 0.2 (for E3 and E2) and 0.5 μg L−1 (for E1), and calibration curves exhibited linearity in the range of 1–1000 μg L−1 with correlation coefficients higher than 0.998. The percent relative standard deviation (RSD) was below 5.0%. Finally, this method was used to determine concentration of estrogens in real lake and sewage water samples. 相似文献
115.
By associating each slice in a spatially homogeneous sample with a different inversion-recovery delay time, multislice methods are used to reduce the acquisition times of 2D inversion-recovery T1-T2 relaxation spectra to just a few minutes. The increased speed comes at the expense of reduced signal/noise and this is reflected most noticeably in shifts in the component longitudinal relaxation times. Nevertheless, the major features of the 2D relaxation spectra are reproduced. 相似文献
116.
Ytterbium chloride (YbCl3) is an effective and reusable catalyst for Diels-Alder reactions of unactivated dienes with α,β-unsaturated ketones and aldehydes at room temperature, leading to products with high regio- and stereoselectivities. 相似文献
117.
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ABSTRACT Four types of mass and frequency optimization problems are stated for free torsional vibration of thin-walled cylinders subject to constraints on wall thickness and frequencies of vibration. It is shown, using Pontryagin's method, that the mathematical structure of all four problems is similar and leads to identical classes of optimal thickness distributions. These duality relations are used in an example to construct an optimal frequency solution from the solutions for both maximum and minimum mass problems. General relations among the governing parameters for the four problems are stated. The results of Grinev and Filippov and of Thermann for the abnormal optimization problems are verfied as a specific limiting example of the general results. 相似文献
120.
An equation been derived to calculate, ab initio, the frequencies and intensities of a resonant Raman spectrum from the transform theory of resonance Raman scattering. This equation has been used to calculate the intensities of the ultraviolet resonance Raman spectra from the first π-π* excited state of uracil and 1,3-dideuterouracil. The protocol for this calculation is as follows: (1) The force constant matrix elements in Cartesian coordinate space, the vibrational frequencies, and the minimum energy ground and excited state geometries of the molecule are calculated ab initio using the molecular orbital program Gaussian 92, (2) the force constants in Cartesian coordinates are transformed into force constants in the space of a set of 3N – 6 nonredundant symmetrized internal coordinates, (3) the G matrix is constructed from the energy minimized ground state Cartesian coordinates and the GFL = LΛ eigenvalue equation is solved in internal coordinate space, (4) the elements of the L and L?1 matrices are calculated, (5) the changes in all of the internal coordinates in going from the ground to the excited state are calculated, and (6) these results are used in combination with the transform theory of resonance Raman scattering to calculate the relative intensities of each of the 3N – 6 vibrations as a function of the exciting laser frequency. There are no adjustable parameters in this calculation, which reproduces the experimental frequencies and intensities with remarkable fidelity. This indicates that the Dushinsky rotation of the modes in the excited state of these molecules is not important and that the simplest form of the transform theory is adequate. © 1995 John Wiley & Sons, Inc. 相似文献