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31.
The metalation of allyl benzyl thioether involves the benzylic or the allylic hydrogens. The benzylic carbanion undergoes a rapid[2,3] sigmatropic shift whereas the allylic carbanion gives rise to various rearrangements, among them migration of the allylic unit to the para position with allylic inversion. The temperature dependence of the ratio of products arising from the benzylic carbanion vs those from the allylic carbanion shows that the allylic-to-benzylic carbanion transformation occurs only under special conditions: (a) with slow addition of the base; (b) with thioether in excess relative to the base, and (c) on raising the temperature of the reaction medium from ?78° to ?15°. In the last instance, the proton transfer is intramolecular as shown with labeled thioethers. The extent of the different rearrangements depends on the temperature and solvent. A choice of mechanism cannot be made at this time for the para migration 5→9a. A leaving group effect on the reaction regioselectivity of the carbanion from allyl methyl thioether with benzyl halides has been noticed. The presence of dibenzyl indicates that, in addition to SN2 reactions, some electron transfer process is occurring. 相似文献
32.
David Ajó Maurizio Casarin Gaetano Granozzi Ignazio Fragalá 《Chemical physics letters》1981,80(1):188-191
The He(I) photoelectron spectra of 5-azauracil (1,3,5-triazine-2,4(1H,3H)-dione) and 6-azauracil (1,2,4-triazine-3, 5(2H,4H)-dione) are presented. The spectra are assigned by using INDO/S calculations and comparison arguments with uracil. The first ionization energy in the title compounds is higher than in the usual nucleic acid bases. 相似文献
33.
34.
John A. Bishop 《Analytica chimica acta》1973,63(2):305-311
Four different methods for the calculation of the formation constants of fluorescing complexes are discussed. The methods were used to determine constants for the complexes of aluminum(III), gallium(III) and indium(III) with 8-quinolinol-5-sulfonate anion. 相似文献
35.
Michael Stavola J.M. Friedman R.A. Stepnoski Mark G. Sceats 《Chemical physics letters》1981,80(1):192-194
Cooperative vibronic spectra involving Gd3+ electronic transitions and the vibrational transitions of nearby water molecules are used to determine the stretching spectrum for isotopically dilute OH in a solution of GdCl3 in D2O. The OH stretching spectrum of water molecules in the first hydration sphere is shifted to lower energy than that of the bulk liquid. 相似文献
36.
Ingemar Wadsö 《Thermochimica Acta》1985,96(2):313-325
The field of isothermal microcalorimetry as applied to systems of interest for aqueous solution chemistry, biochemistry and in cellular biology is briefly reviewed. Some techniques recently developed in the author's laboratory are described. 相似文献
37.
Solvent shift in water of π → π* transitions of the carbonyl group is evaluated making use of a recently proposed computdtional procedure for the continuum solvent model. Comparisons with the discrete model and with composite discrete-continuum procedures are performed. 相似文献
38.
An electrochemical method has been developed for determining the relative amounts of V(II) and V(III) in polyolefin catalysts prepared using aluminum alkyls and vanadium trichloride. The catalyst, usually obtained as a slurry in n-heptane, is titrated potentiometrically with ceric sulfate using a platinum indicator electrode. Under proper experimental conditions, 2 breaks are obtained, corresponding to the reactions V(II) →V(III) + e and V(III) →V(IV) + e. Interferences from other components of the catalyst are negligible. The method is useful for the analysis of both laboratory catalysts and grab samples taken from pilot plant reactors. 相似文献
39.
Reaction of bicyclo[3.2.2] tertiary alcohols 7b,c and 23b with Fe2(CO)9, resulted in the corresponding dienyl Fe(CO)3 complexes, which upon HBF4/Ac2O treatment yielded the bicyclo [3.2.2] dienyl irontricarbonyl cations. Nucleophilic addition of CN- to those cations, resulted in the formation of δ,μ-bonded complexes, which were degraded with Me3NO to give substituted tricydic hydrocarbons (barbaralyl systems) in unusual positions. For purpose of comparison, the trifluoroacetolysis of 2-methyl-endo-6,7-benzobicyclo[3.2.2] nonatriene (22) has been studied. 相似文献
40.
Kikuo Miyokawa Masayuki Itoh Takummi Etoh Setsuko Kinoshita Isao Masuda 《Thermochimica Acta》1985,96(1):227-234
Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me2 (4), 3,5-Me2 (5), 3-NH2 (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed. 相似文献