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71.
Yutaka Sawada Junji Yamaguchi Osamu Sakurai Keizo Uematsu Nobuyasu Mizutani Masanori Kato 《Thermochimica Acta》1979,34(2):233-237
An exothermic phenomenon and a simultaneous rapid evolution of a small amount of carbon dioxide at ?500°C during thermal decomposition of hydromagnesite 4 MgCO3 · Mg(OH)2 · 4 H2O was studied by isothermal DSCTG in a carbon dioxide atmosphere. It was quantitatively confirmed that the exothermic phenomenon was due to crystallization of MgCO3 from the amorphous phase and that the evolution of carbon dioxide was due to decomposition of the MgCO3 by the heat of crystallization (?3.4 kcal mole?1. 相似文献
72.
Tadamasa Shida Yasufumi Takahashi Hiroyuki Hatano Masashi Imamura 《Chemical physics letters》1975,33(3):491-494
Radical-anions of iodine, bromine, and monoiodochloride are produced in γ-irradiated amorphous solids at 77 K, and their electronic and ESR spectra measured. On limited warming of the irradiated solution dimerization by the reaction I2? + I2 → I4? occurs to produce the same species as reported by Fornier de Violet et al. The electronic structure of the dimeric anion is discussed in comparison with the monomeric anion. 相似文献
73.
Kizashi Yamaguchi 《International journal of quantum chemistry》1982,22(3):459-484
A generalization of the Hartree–Fock molecular orbital (MO) theory for treating diradical intermediates was explained pictorially by drawing molecular orbitals of diradical species such as ring-opened trimethylene. The generalized MO theory applied to elucidate electronic mechanisms of concerted, ionic, radical, and ion-radical reactions of organic reactants in the ground state. Generalized MO computations revealed the most essential characteristics of these reactions and mutal relationships between the worlds of Woodward–Hoffmann and Hughes–Ingold. Generalized MO studies supported our orbital symmetry, stability and pairing rules for concerted, ionic and radical reactions in the ground state, respectively. An extension of MO treatments to excited states reactions was briefly pointed out in relation to the density and spin correlation functions by the multireference CI wave functions. 相似文献
74.
Electronic structures and spectra of Hafner's hydrocarbons have been calculated by means of the semi-empirical SCF CI MO method incorporated with the variable bond-length technique. The results are in good agreement with experimental data. 相似文献
75.
Masashi Hamaguchi Kazuma TakahashiTakumi Oshima Hatsue Tamura 《Tetrahedron letters》2003,44(23):4339-4342
Reactions of tricarbonyl compounds with vinyl diazo compounds 2 were carried out. Reaction of 1,2,3-indanetrione with 2a,b,c gave the spiroindan-1,3-dione-2,2′-benzodihydrooxepin 7a,b,c, but not normal products oxirane and dihydrofuran derivatives expected from intermediate vinyl carbonyl ylides 4. Formation of 7 requires isomerization of vinyl carbonyl ylides 4 bearing a (Z)-cyanostyryl group to unstable (E)-form 5 and subsequent cyclization to oxepin 6 followed by a 1,5-hydrogen shift. However, reaction of 2 with six-membered cyclic tricarbonyl compounds 1,2,3-trioxo-2,3-dihydrophenalene 11 and dimethylalloxane 13 gave the dioxole 12 and the dihydrofuran 14, respectively, typical products expected from vinyl carbonyl ylides. 相似文献
76.
Electrophoretic analysis of quinone anion radicals in acetonitrile solutions using an on-line radical generator 总被引:1,自引:0,他引:1
We have investigated analysis of anion radicals of phenanthrenequinone (PhQ) and anthraquinone (AQ) using acetonitrile-capillary electrophoresis (CE) under anaerobic conditions. PhQ and AQ have relatively high negative reduction potentials meaning that their anion radicals are re-oxidized quite readily by the surrounding O(2) to disappear during analysis and we failed to detect them with our previous system. In this work, we have developed an on-line system combining a unique electrolysis cell for generation of the radicals and a CE unit to keep the analysis system free from external O(2) molecules and to reduce analysis time remarkably. As a result, electrophoretic detection of the anion radicals of PhQ and AQ has been achieved. Furthermore, we have observed hydrogen-bonding interaction between the anion radicals and dimethylurea (DMU) using the present system and have indicated a characteristic interaction of the anion radical of PhQ as an ortho-quinone with DMU. 相似文献
77.
The constitution of Grignard reagent, RMgCl (R = Me, tBu, Ph or benzyl), was investigated in the solid state by means of X-ray crystallography and in THF by coldspray ionization mass spectrometry (CSI-MS). Three types of crystal structures, (a) [Mg2(mu-Cl3)(THF)6](+)*[RMgCl2(THF)](-), (b) R2Mg4Cl6(THF)6, and (c) [2Mg2(mu-Cl3)(THF)6](+)*[R4Mg2Cl2]2-, were identified, and MeMg2(mu-Cl3)(THF)4-6 were detected as major species of MeMgCl in solution. 相似文献
78.
Miyauchi M Hoshino T Yamaguchi H Kamitori S Harada A 《Journal of the American Chemical Society》2005,127(7):2034-2035
A [2]rotaxane capped by a beta-cyclodextrin and a 2,4,6-trinitrophenyl group has been prepared by dissolving 6-aminocinnamoyl beta-cyclodextrin in water with 1-adamantane carboxylic acid and complexation with alpha-cyclodextrin followed by the reaction with 2,4,6-trinitrobenzene sulfonic acid sodium salt. The [2]rotaxane has been found to form supramolecular polymers by host-guest interactions. 相似文献
79.
80.
The reaction of zirconium n-propoxide in glycol at 300°C yielded microcrystalline tetragonal zirconia (ZrO2). The crystallite size of the product depended on the carbon number of the glycol and increased in the following order (carbon
number of glycol): 2<6<4, which suggested that the heterolytic cleavage of O-C bond of gylcoxide formed by transesterification
is the prime factor for the formation of the product. In toluene, zirconium isopropoxide also gave tetragonal zirconia at
300°C, and zirconium tert-butoxide decomposed at 200°C yielding amorphous zirconia, while zirconium n-propoxide was stable at 300°C. These results suggest that the reaction in toluene depends on the structure of the alkyl group
of the alkoxides. Thus-obtained tetragonal zirconias maintained large surface areas (90–160 m2/g) even after calcination at 500°C. 相似文献