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31.
In this work, a simple, fast and reproducible method is presented for the determination of fibre/liquid-phase and fibre/gas-phase
partition coefficients of five chlorinated ethenes on a poly-(dimethylsiloxane), PDMS-coated, solid-phase microextraction
fibre, by employing a headspace HS-SPME coupled with gas chromatography. The partition coefficients were estimated by a numerical
method using a Level-I fugacity method coupled with parameter-estimation software. Dimensionless partition coefficients between
SPME fibre and liquid as well as gas phases were obtained at temperatures of 10 °C, 25 °C and 30 °C. The partition coefficients
of the fibre and the gas phase, K
fg, increase with decreasing temperature by a factor of ≈2 to 6, and they are directly proportional to the linear slope of the
regression line. The same tendency is observed for the partition coefficient of the fibre and liquid phase, K
fw, in a factor ≈1.2 to 2.0. The sorption enthalpy is higher in the gas phase; therefore, the sorption onto the fibre is favoured
at lower temperatures. The correlation of the log K
ow versus log K
fw and log K
oa versus log K
fg shows a linear relationship with the number of chlorine atoms in the C = C molecule. Long-term experiments resulted in sorption
to Teflon surfaces and possible losses in 43 mL vials, not observed in 250 mL Boston bottles. 相似文献
32.
Ignacio H. Sánchez María Isabel Larraza Fernande Basurto Ricardo Yaf?ez Salvador Avila Ricardo Tovar Pedro Joseph-Nathan 《Tetrahedron》1985,41(12):2355-2359
(±)--methylperezone () was obtained by selective oxidative demethylation of (±)-leucoperezone trimethyl ether (). Compound () was prepared by condensation of 2,3,5-trimethoxytoluene () with 6-methyl-5-hepten-2-one, followed by reductive removal of the tertiary alcohol. The aromatic precursor was prepared in four steps from 2,3-dimethoxytoluene () and, alternatively, in three steps from 5-bromoveratraldehyde (). Racemic and were directly compared with the optically active molecules prepared from natural R(-)-perezone (). 相似文献
33.
A sequential injection UV method was developed to determine benzophenone-4 (BZ4) and phenylbenzimidazole sulphonic acid (PBS) simultaneously, these being the most commonly used UV-filters in aqueous formulations used as sunscreen sprays. The selective elution of both was performed by on-line solid-phase extraction, by retention on a SAX microcolumn and separation by varying the pH of elution. The sensitivity obtained was 0.042±0.001 ml μg−1 for PBS and 0.0159±0.0003 ml μg−1 for BZ4. The limit of detection was 1.6 μg ml−1 for PBS and 0.6 μg ml−1 for BZ4. The R.S.D. of the results was 1-6% for PBS and 1-12% for BZ4. The method was validated using commercial sunscreen formulations with concentrations determined by a liquid chromatographic procedure. The two procedures gave comparable results. Automation of the method means the amount of reagents used and residues generated are decreased. The system allows the required analysis sequence to be programmed using suitable software. 相似文献
34.
The synthesis of the title compounds was carried out by cyclization via isocyanate of (E)-4,5-dihydro-10H-benzo[5,6]cyclohepta[1,2-b]-thiophene-10-ylideneacetic acid and 4,5-dihydro-10H-benzo[5,6]cyclohepta[1,2-b]-thiophene-10-ylacetic acid respectively, which were obtained by the Wadsworth-Emmons modification of the Wittig reaction of 4,5-dihydro-10H-10-oxobenzo[5,6]cyclohepta[1,2-b]thiophene and triethyl phosphonacetate. The structures of these new compounds are described. 相似文献
35.
The present work provides a generalization of Mayer's energy decomposition for the density-functional theory (DFT) case. It is shown that one- and two-atom Hartree-Fock energy components in Mayer's approach can be represented as an action of a one-atom potential V(A) on a one-atom density rho(A) or rho(B). To treat the exchange-correlation term in the DFT energy expression in a similar way, the exchange-correlation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and Hartree-Fock two-atom energies agree to a reasonable extent with each other. The two-atom energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules. For nonspecific nonbonding interactions, the two-atom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the Hartree-Fock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale. 相似文献
36.
Determination of pirimicarb and endosulfan in commercial pesticide formulations by Fourier transform infrared spectrometry 总被引:1,自引:0,他引:1
Quintás G Moros J Armenta S Garrigues S de la Guardia M 《Journal of AOAC International》2005,88(2):399-405
A routine method based on Fourier transform infrared spectrometry was developed for the simultaneous determination of pirimicarb and endosulfan in commercially available pesticide formulations. The method is based on peak area absorbance measurements between 1362 and 1352 cm(-1), corrected with a baseline fixed at 1338 cm(-1), for pirimicarb and peak area absorbance measurements between 919 and 909 cm(-1) with a baseline fixed at 931 cm(-1) for endosulfan; chloroform solutions for analysis were obtained by direct dilution of emulsifiable concentrates or by solvent extraction from solid samples. Various extraction conditions and appropriate band selection were investigated, and interference studies were performed. Under the experimental conditions selected, limits of detection of 13 microg/g for pirimicarb and 150 microg/g for endosulfan were obtained that correspond to 0.13 and 1.6% (w/w), respectively, in commercial samples. Results from analyses of commercial samples by the developed method compared well with those obtained by a liquid chromatography reference method. 相似文献
37.
Christian Borgs Roman Kotecký Salvador Miracle-Solé 《Journal of statistical physics》1991,62(3-4):529-551
Recently, Borgs and Kotecký developed a rigorous theory of finite-size effects near first-order phase transitions. Here we apply this theory to the ferromagneticq-state Potts model, which (forq large andd2) undergoes a first-order phase transition as the inverse temperature is varied. We prove a formula for the internal energy in a periodic cube of side lengthL which describes the rounding of the infinite-volume jumpE in terms of a hyperbolic tangent, and show that the position of the maximum of the specific heat is shifted by
m
(L)=(Inq/E)L
–d
+O(L
–2d
) with respect to the infinite-volume transition point
t
. We also propose an alternative definition of the finite-volume transition temperature
t
(L) which might be useful for numerical calculations because it differs only by exponentially small corrections from
t
. 相似文献
38.
Zully A. Benzo Manuelita Velosa Claudio Ceccarelli Miguel Guardia Amparo Salvador 《Fresenius' Journal of Analytical Chemistry》1991,339(4):235-239
Summary The literature on the application of the slurry technique to biological materials is reviewed. It is obvious from the various applications that the most frequently employed atomization method for slurry analysis in biological materials is electrothermal atomization using either graphite tube or platform atomizers. The slurry technique is particularly useful when certified reference materials are not available and when the standard addition method is to be avoided. The literature survey revealed that this technique compares favourably with other methods for the determination of trace metals in biological materials. 相似文献
39.
40.
A fast procedure has been developed for the direct determination of paint solvents. The method is based on the injection of small volumes of untreated solvent mixtures into a heated Pyrex glass reactor in which the sample is volatilized and introduced by means of a flow of nitrogen into an IR multiple pass gas cell and the spectrum in the mid-IR region is registered as a function of time. Data found for samples are interpolated in calibration graphs obtained by injecting different volumes of pure compounds which constitute the solvent mixture. A methylisobutylketone (MIBK) toluene mixture was used as test system to develop the proposed procedure. The method provides a limit of detection of the order of 1–4 μg, a relative standard deviation of the order of 0.4 to 2% for five independent measurements, and recovery percentage values from 99.8 till 103.6 %. A commercial sample of polyurethane paint solvent has been analysed by the developed procedure. 相似文献