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21.
The examination of 19F chemical shifts for ca. 650 F-alkylated compounds of general formula CF3(CF2)nCF2X led to the following conclusions: the CF2 groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF2(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF2(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds. 相似文献
22.
A study of the trapping of highly pyramidalized tricyclo[3.3.0.03,7]oct-1(5)-ene derivatives (generated from a 1,2-diiodo precursor on reaction with t-BuLi, 0.45% sodium amalgam and molten sodium) with different dienes (11,12-dimethylene-9,10-dihydro-9,10-ethanoanthracene, 1,3-diphenylisobenzofuran, 2,5-dimethylfuran and furan) is presented. Byproducts from the trapping of pentacyclo[6.4.0.02,10.03,7.04,9]dodeca-5,8,11-triene with 1,3-diphenylisobenzofuran have been synthesized and fully characterized, including an X-ray diffraction analysis. Also, the above triene has been cross coupled with 3,7-dimethyltricyclo[3.3.0.03,7]oct-1(5)ene to give a tetrasecododecahedratetraene derivative. 相似文献
23.
Ichiya Ninomiya Toshiko Kiguchi Chiyomi Hashimoto Derek H.R. Barton Xavier Lusinchi Pierre Milliet 《Tetrahedron letters》1985,26(35):4183-4186
The addition of a sacrificial enamine (such as indole), or of a vinyl ether (like dihydropyran) to an indoline during dehydrogenation by phenylseleninic anhydride dramatically improves the yield of the corresponding indole. This is due to scavenging of Se11 phenylselenenating species. 相似文献
24.
Fluorescence quenching of a thioxanthone derivative by methyl- and methoxy-substituted benzenes (MeB and MeOB, respectively) is performed in solvents of different polarity. Emissive exciplexes are observed even in polar solvents and provide kinetic and spectroscopic data over a large scale of solvent polarity. These data were subsequently analyzed by use of a new theoretical model that leads to a thermodynamic relationship between exciplex and electron-transfer driving forces Delta G(exc) and Delta G(et), respectively. The remarkable agreement found between this model and both kinetic and spectroscopic data supports its validity. Moreover, the difference observed between MeB and MeOB compounds in quenching efficiency is analyzed by this model and provides the main parameters governing exciplex features, especially the resonance integral between locally excited and charge-transfer states. 相似文献
25.
The considered mathematical model of the decomposition of valerate presents three unknown kinetic parameters, two unknown
stoichiometric coefficients, and three unknown initial concentrations for biomass. Applying a structural identifiability study,
we concluded that it is necessary to perform simultaneous batch experiments with differenitial conditions for estimating these
parameters. Four simultaneous batch experiments were conducted at 55°C, characterized by four different initial acetate concentrations.
Product inhibition of valerate degradation by acetate was considered. Practical identification was done optimizing the sum
of the multiple determination coefficients for all measured state viariables and for all experiments simultaneously. The estimated
values of kinetic parameters and stoichiometric coefficients were characterized by the parameter correlation matrix, the confidence
interval, and the student's t-test at 9% significance level with positive results except for the saturation constant, for which more eperiments for improving
its identifiability should be conducted. In this article, we discussekinetic parameter estimation methods. 相似文献
26.
J. C. Y. Le Blanc D. Beuchemin K. W. M. Siu R. Guevremont S. S. Berman 《Journal of mass spectrometry : JMS》1991,26(10):831-839
The effects of beat on the electrospray mass spectra of eight globular proteins in solution were studied. These ranged from hardly noticeable to a dramatic shift in the mass spectrometric profile and a concomitant increase in ion abundance. This change is believed to be the result of thermal denaturation of the protein species in solution resulting in a transition from a more compact to a less compact conformation. We accounted for this transition by means of a recently proposed model based on aqueous solution acid/base equilibria. For cytochrome c, profiles calculated by means of this model agree well with experimental data. The ΔH of the denaturation reaction of cytochrome c in aqueous solution containing 0.2% acetic acid was calculated from experimental data to be 103.8 ± 9.2 kJ mol?1, in good agreement with previous measurements. 相似文献
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Equilibrium constants for oxidations of cyclanols by cyclohexanone in benzene have been determined in the presence of aluminium isopropoxide. The free energies of the equilibrium (ΔGox) are correlated with equilibrium constants for dissociation of cyanohydrins, rate constants for cyclanol oxidation with chromic acid, ketone reduction with sodium borohydride and trifluoroethanolysis of tosylates. 相似文献