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111.
A laser ablation-inductively coupled plasma-mass spectrometric (LA-ICPMS) technique utilizing a titanium-sapphire (TiS) femtosecond laser (fs-laser) has been developed for elemental and isotopic analysis. The signal intensity profile, depth of the ablation pit and level of elemental fractionation were investigated in order to evaluate the analytical capability of the present fs-laser ablation-ICPMS technique. The signal intensity profile of (57)Fe, obtained from iron sulfide (FeS(2)), demonstrated that the resulting signal intensity of (57)Fe achieved by the fs-laser ablation was almost 4-times higher than that obtained by ArF excimer laser ablation under a similar energy fluence (5 J/cm(2)). In fs-laser ablation, there is no significant difference in a depth of the ablation pit between glass and zircon material, while in ArF laser ablation, the resulting crater depth on the zircon crystal was almost half the level than that obtained for glass material. Both the thermal-induced and particle size-related elemental fractionations, which have been thought to be main sources of analytical error in the LA-ICPMS analysis, were measured on a Harvard 91500 zircon crystal. The resulting fractionation indexes on the (206)Pb/(238)U (f(Pb/U)) and (238)U/(232)Th (f(U/Th)) ratios obtained by the present fs-laser ablation system were significantly smaller than those obtained by a conventional ArF excimer laser ablation system, demonstrative of smaller elemental fractionation. Using the present fs-laser ablation technique, the time profile of the signal intensity of (56)Fe and the isotopic ratios ((57)Fe/(54)Fe and (56)Fe/(54)Fe) have been measured on a natural pyrite (FeS(2)) sample. Repeatability in signal intensity of (56)Fe achieved by the fs-laser ablation system was significantly better than that obtained by ArF excimer laser ablation. Moreover, the resulting precision in (57)Fe/(54)Fe and (56)Fe/(54)Fe ratio measurements could be improved by the fs-laser ablation system. The data obtained here clearly demonstrate that, even with the fundamental wavelength (NIR operating at 780 nm), the fs-laser ablation system has the potential to become a significant tool for in-situ elemental and isotopic analysis of geochemical samples including heavy minerals and metallic materials. 相似文献
112.
[reaction: see text] The first catalytic asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones has been developed by way of a rhodium-catalyzed 1,4-addition of arylzinc reagents to 4-quinolones. These 1,4-adducts can be obtained with high enantioselectivity by the use of (R)-binap as a ligand, and high yields are realized by conducting the reactions in the presence of chlorotrimethylsilane. 相似文献
113.
Choji Kashima Isanobu Kita Katsumi Takahashi Akira Hosomi 《Journal of heterocyclic chemistry》1995,32(1):25-27
N-Acylpyrazoles afford chemoselectively the corresponding ketones in good yields by the use of equimolar amounts of Grignard reagent. In the case of an optically active N-acylpyrazole, optical asymmetry was retained in comparable optical yield. Ketone formation by the Grignard reactions can be regarded as an important functionalization in a synthetic loop using pyrazoles as the auxiliary compound. 相似文献
114.
Takafumi Uematsu Shinya Maenosono Akira Watanabe Yukio Yamaguchi 《Journal of Polymer Science.Polymer Physics》2002,40(2):216-225
We report on a self‐organized striped pattern of refractive indices in a photopolymer and the resulting angular dependence in the transmittance as a result of the microstructure. The photopolymer plates were obtained by photoreaction of a monomer mixture placed in a space between two glass plates. The monomer mixture was prepared by mixing bifunctional methacrylate monomer, cyanoethylmethacrylate, and 2,4,6‐trimethylbenzoyldiphenylphosphine oxide as photoinitiator. After the photoreaction by uniform irradiation of UV light, the self‐organized striped pattern was observed in the crosslinked photopolymer plate by optical microscopy. Electron probe microanalysis of the cross section of the polymer plate confirms that a compositional inhomogeneity in the medium is quite small. The result suggests that the optically observed striped pattern is not due to the compositional and/or density modulation through the diffusion of monomers. We attribute the striped pattern to the crosslink density modulation and the resulting refractive‐index modulation. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 216–225, 2002 相似文献
115.
The effects of the metallurgical structure and the aluminium content of copper—aluminium alloy (1–12% Al) on the sputtering and intensities of spectral lines in the Grimm glow lamp are reported. The electrical current and sputtering yield decreased linearly with increasing aluminium content; the intensities of the Al I lines depended linearly on the amount of aluminium in the sputtering yield at a fixed voltage and argon pressure. The structure affected the intensities of the Al I and Cu I lines but not the intensity ratio (Al I/Cu I) for about 100 s after burn-off. Working curves for aluminium for samples of different structure were very similar. 相似文献
116.
Chiral calixarene analogs incorporating cystine peptide into their macrocyclic ring were easily prepared by the cyclization reactions of bis(chloromethyl)phenol-formaldehyde oligomers with cystine peptides in moderate yields. Circular dichroism (CD) spectra indicated the existence of the transmission of the chirality from peptide unit to phenol-formaldehyde oligomer moiety. 相似文献
117.
Yoshitane Imai Takafumi Kinuta Nobuo Tajima Yoshio Matubara 《Tetrahedron letters》2006,47(21):3603-3606
By using three types of viologen derivatives, we synthesized chiral charge-transfer (CT) complexes with an axially chiral 1,1′-bi-2-naphthol molecule and successfully controlled the crystal structure and inclusion ability of the third component by changing the viologens. 相似文献
118.
Takafumi Shido Takumi Okazaki Masaru Ichikawa 《Journal of molecular catalysis. A, Chemical》1997,120(1-3):33-45
Structure and catalytic activity of Ir4(CO)12 bound to tris-(hydroxymethyl)phosphine (THP) grafted silica (THP/SiO2) was investigated by means of EXAFS, FT-IR and kinetic studies. It was found that Ir4(CO)12 was uniformly attached on THP/SiO2 by substitution of CO by THP (Ir4/THP/SiO2). The tetra-iridium carbonyl cluster framework was remained during the substitution of THP ligands and two THP ligands coordinated to the iridium carbonyl clusters to form Ir4(CO)10(THP/SiO2)2. species. When Ir4/THP/SiO2 was evacuated at 373 K, bridge CO was desorbed and Debye-Waller factor of Ir---Ir contribution derived from EXAFS analysis was increased which suggested that the cluster framework was distorted by the evacuation at 373 K. The resulting sample evacuated at 373 K was an active catalyst for hydroformylation of ethene and partial oxidation of propene, while the Ir4/THP/SiO2 without evacuation exhibited poor catalytic activities. The propene oxidation reaction proceed on the Ir4/THP/SiO2 evacuated at 323–353 K under subatmospheric pressures to give acetone as a product in high selectivity. The ethene hydroformylation proceed on the evacuated Ir4/THP/SiO2 at lower temperatures compared with other conventional iridium catalysts. EXAFS characterization and kinetic studies suggested that the catalytic activities were associated with the structural distortion of the iridium cluster framework due to surface attachment by the bidentate phosphine substitution. 相似文献
119.
Three antibiotics with a common structural feature as prenylated phenols were synthesized: (±)-ascochlorin (5 - chloro-2,4 - dihydroxy - 6 - methyl - 3 - [(2E',4/E') - 5' - (1′,2′,6′ - trimethyl - 3′-oxocyclohexyl) - 3' - methyl - 2',4' - p benzaldehyde), (±)-ascofuranone (5 - chloro - 2,4 - dihydroxy - 6 - methyl - 3 - [(2'E,6'E) - 7' - (3′,3′ - dimethyl - 4′ - oxo - 2′ - oxacyclopentyl) - 3',7 -dimethyl - 2',6' - heptadienyl] benzaldehyde) and LL-Z1272α (5 - chloro - 2,4 - dihydroxy - 6 - methyl -3 - [(2'E,6'E) - 3',7',11' - trimethyl - 2',6', 10' - dodecatrienyl] benzaldehyde) 相似文献
120.