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71.
微波固相法合成钠快离子导体Na5YSi4O12 总被引:6,自引:0,他引:6
应用微波方法合固相反应难于制备的Na5YSi4O12纯相,讨论了微波合成条件对产物的影响,与溶胶-凝胶法相比,微波法反应速率快,选择性强,合成的样品具有特异的聚集态,缺陷和微结构,从而导致离子导电活化能下降。 相似文献
72.
Interactions between divalent alkali earth metal (DAEM) ions M (M?Be, Mg, Ca, Sr, Ba) and the second stable glycine conformer in the gas phase, which can transfer into the ground‐state glycine‐M2+ (except the glycine–Be2+) among each corresponding isomers when these divalent metal ions are bound, are studied at the hybrid three‐parameter B3LYP level with three different basis sets. Proton transfers from the hydroxyl to the amino nitrogen of the glycine without energy barriers have been first observed in the gas phase in these glycine–M2+ systems. The interaction between the glycine and these DAEM ions except beryllium and magnesium ion only create an amino hydrogen pointing to the original hydroxyl due to their weaker interaction relative to those divalent transition metal (DTM) ion‐bound glycine derivatives, being obviously different from that between the glycine and DTM ions, in which two amino hydrogens point to the original hydroxyl oxygen when these metal‐chelated glycine derivatives are produced. The interaction energy between the glycine and divalent magnesium would be the boundary of one or two amino hydrogens pointing to the hydrogyl oxygen, i.e., the ?170.3 kcal/mol of binding energy is a critical point. Similar intramolecular proton transfer has also been predicted for those DTM ion‐chelated glycine systems; however, that in the gas state has not been observed in the monovalent metal ion‐coordinated glycine systems. The binding energy between some monovalent TM ion and the glycine is similar to that of the glycine–Ba2+, which has the lowest binding strength among these DAEM–ion chelated glycine complexes. The difference among them only lies in the larger electrostatic and polarized effects in the latter, which favor the stability of the zwitterionic glycine form in the gas phase. According to these observations, we predict that the zwitterionic glycine would exist in the field of two positive charges in the gas phase. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 205–214, 2003 相似文献
73.
The force fields, in-plane vibrations, and relative intensities of Raman spectra have been calculated and analyzed for the N1H and N3H tautomers of imidazole, imidazolium cation, and their model structures. The results obtained for the isolated state of imidazole correspond to the intramolecular mechanism of proton transfer. 相似文献
74.
In this work we address the optimization of mixed conductivity in fluorite compounds based on zirconia. Phase relations of the new systems YbO1.5-NbO2.5-ZrO2, and CaO-NbO2.5-ZrO2 are presented. The limit of the cubic defect fluorite phase in YbO1.5-NbO2.5-ZrO2 closely resembles that of the system YO1.5-NbO2.5-ZrO2, whilst in CaO-NbO2.5-ZrO2 is narrow extending to include composition Ca0.255Nb0.15Zr0.595O1.82 at 1500°C. The influence of dopant ion size, charge and composition on ionic conduction is assessed and parallels are drawn with the systems YO1.5-NbO2.5-ZrO2 and YO1.5-TiO2-ZrO2. Comparison of these results with published data on the Ti containing systems CaO-TiO2-ZrO2, GdO1.5-TiO2-ZrO2 shows that the highest mixed conducting compositions can only be offered in the system YO1.5-TiO2-ZrO2 out of all the systems here studied. 相似文献
75.
Lakshminarasimhan Damodharan 《Tetrahedron letters》2004,45(51):9427-9429
Database analysis on H ? H interactions of the type CH2 ? H2C and N-H ? H-N in organic crystals substantiate the occurrence of dihydrogen bonds in the absence of metal atoms. 相似文献
76.
The semi-empirical quantum chemical MNDO-PM3 calculations of the enthalpies of formation of Meisenheimerortho- andipso--complexes of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) with the phenoxide anion in the gas phase and in water are performed within the framework of the point dipole model. Based on the calculated heats and activation barriers to substitution of the nitro group by the phenoxyl group in TNB and TNT, the possibility of the reactions of TNB and TNT with the phenoxide anion in water is shown. These reactions in water occurvia the SNAr mechanism involving the correspondingipso--complex as an intermediate. In the gas phase, the SNAr mechanism is impossible, because the reaction is strongly endothermic. In the case of TNT, the exothermic reaction of elimination of a proton from the methyl group by the phenoxide anion competes with nucleophilic substitution in a polar solvent. The activation energy calculated for this exothermic reaction is 8 kcal mol–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 624–628, April, 1995. 相似文献
77.
A new organic photochromic compound containing pyrazolone-ring photochromic functional unit: 1-phenyl-3-methyl-4-benzyl-5-one pyrazole S-methyl thiosemicarbazone (PMBP-smtsc) was synthesized. The photochromic properties and photochemical kinetics of PMBP-smtsc have been studied by UV reflectance spectra under irradiation of 365 nm light. The crystal structure analyses of photocolored product show the photochromism is due to the photoisomerization from enol form to keto form through an intermolecular proton transfer. 相似文献
78.
In this paper, 2-(2′-hydroxy-phenyl)-4(3H)-quinazolinone (HPQ), a typical compound that exhibits excited state intramolecular proton transfer (ESIPT) reaction and possesses good photophysical properties, is synthesized and used as fluoroionophore for Fe3+ sensitive optochemical sensor. The decrease of fluorescence intensity of HPQ membrane upon the addition of Fe3+ was attributed to the blocking of ESIPT reactions of HPQ and quenching its fluorescence. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensor shows a linear response toward Fe3+ in the concentration range of 7.1 × 10−7 M to 1.4 × 10−4 M with a limit of detection of 8.0 × 10−8 M, and a working pH range from 2.5 to 4.5. It shows excellent selectivity for Fe3+ over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed sensor is applied to the determination of the content of iron ions in pharmaceutical preparations samples with satisfactory results. 相似文献
79.
多嵌段聚醚氨酯脲为基质的新型高分子固态离子导体 总被引:2,自引:0,他引:2
本文合成了一系列聚乙二醇型多嵌段聚醚氨酯脲,而且用这类聚醚氨酯甩与高氯酸锂制得了一种新型的高分子固态离子导体复合物。在室温和50℃之间,其电导率比聚环氧乙烷为基质的固体电解质的高一到二个数量级,它还具有优良的综合性能。因此,对于室温薄膜蓄电池来说,这种新型的固体电解质是一类良好的候选材料。 相似文献
80.