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61.
The intramolecular attack of carbanions to oxetanes were examined and several three, five, and six membered carbocyclic compounds were synthesized. 相似文献
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A catalytic pinacol coupling using water as a solvent was performed by a catalytic amount of vanadium(III) chloride and metallic Al as a co-reductant. A combination forms a binary catalytic system, being in sharp contrast to the reaction in organic solvent, which requires a chlorosilane as an additive. Various aromatic aldehydes underwent the reductive coupling to give the corresponding 1,2-diols in moderate to good yields. 相似文献
66.
Zhao Y Higashihara T Sugiyama K Hirao A 《Journal of the American Chemical Society》2005,127(41):14158-14159
Novel 3-arm ABC, 4-arm ABCD, and 5-arm ABCDE asymmetric star polymers comprising the conductive polyacetylene precursor, poly(4-methylphenyl vinyl sulfoxide) (PMePVSO), and other segments, such as polystyrene, poly(alpha-methylstyrene), poly(4-methoxystyrene), poly(4-trimethylsilylstyrene), and poly(4-methylstyrene), were synthesized by the methodology based on living anionic polymerization using DPE-functionalized polymers. This methodology involves the addition reaction of a DPE-functionalized polymer to a living anionic polymer followed by the living anionic polymerization of MePVSO initiated from the in situ formed polymer anion with two, three, or four polymer segments. The resultant asymmetric star polymers possessed predetermined molecular weights, narrow molecular weight distributions (Mw/Mn < 1.03), and desired compositions as confirmed by SEC, 1H NMR, SLS, and elemental analysis. After thermal treatment, the PMePVSO segment in the star polymer could be completely converted into a conductive polyacetylene segment, evident from TGA and elemental analysis. These asymmetric star polymers are expected to exhibit interesting solution properties and unique microphase-separated morphological suprastructures with potential applications in nanoscopic conductive materials. Moreover, this methodology can afford the target asymmetric star polymers with arm segments varying in a wide range and enables the synthesis of more complex macromolecular architectures. 相似文献
67.
Kenzo Ohkita Hideo Kurosawa Toshikazu Hirao Isao Ikeda 《Journal of organometallic chemistry》1994,470(1-2):189-190
Relative stability in coordination of substituted styrene derivatives to [Ru(η-C5H5)(dtpe)]+ (dtpe = 1,2-bis(di-p-tolylphosphino)-ethane) was determined by NMR spectroscopy to reveal unusually weak substituent dependency of the stability. 相似文献
68.
A new dendritic oligoarylamine, N,N,N',N',N",N"-hexakis[4-(di-4-anisylamino)phenyl]- 1,3,5-benzenetriamine (BTA) 2, which contains a 1,3,5-benzenetriamine molecular unit as an potential precursor of a high-spin molecule and three oligoarylamine moieties as spin-carrying units surrounding the core BTA, has been prepared by the sequential palladium-catalyzed amination reactions. The redox property has been investigated by cyclic voltammetry, and the highly charged states up to the hexacation are accessible to 2. The polycationic high-spin species have been generated by stepwise chemical oxidation, and the electronic structures have been examined in detail by the continuous wave (CW) and pulsed ESR spectroscopy in comparison with the previously studied 1. The pulsed ESR technique enabled us to determine the definite spin multiplicity of the generated polycationic species of 2. It was confirmed that the dominant oxidized species observed by the two- and three-electron oxidations were assigned to the spin triplet 2(2+) and the spin quartet 2(3+), respectively. Moreover, these high-spin polycationic species turned out to be far more stable as compared to 1, and the isolation of 2(3+) as the SbCl(6)(-) salt has been accomplished. The temperature dependence of the magnetic susceptibility for the 2(3+)(SbCl(6)(-))(3) salt revealed that the intramolecular ferromagnetic interaction exists in 2(3+), and moreover, the trication 2(3+) was found to be deformed in the solid state. 相似文献
69.
A method for analyzing the A(1u)/A(2u) contents of metalloporphyrin pi-cation radicals is developed and applied to a series of unsubstituted planar metalloporphines (MPs) (M=Cr, Mn, Fe, Co, Ni, Cu, and Zn). The structures and electronic properties of the MPs and their cation radicals were calculated by density functional theory (DFT) and subsequently analyzed. It was found that the MPs with small core sizes have a tendency to form A(1u)-type radicals, while the MPs with large core size have a preference for an A(2u)-type. Neither of these pure-state species, however, is stable under the D(4)(h) symmetry, and both radical cation types are subject to pseudo-Jahn-Teller (pJT) distortion. The pJT distortion leads to structures with lower symmetry and states that have mixed character with respect to the A(1u) and A(2u) components. The degree of mixing could be estimated by employing orbital projection technique or a complementary spin density decomposition. Both techniques produce very similar results, pointing out that the frontier orbital, which becomes empty upon electron removal, plays a critical role in determining electronic properties. 相似文献
70.
Tokiyoshi Matsuda Mamoru Furuta Takahiro Hiramatsu Hiroshi Furuta Chaoyang Li Takashi Hirao 《Applied Surface Science》2010,256(21):6350-2485
Thermal stability of sputter deposited ZnO thin films was evaluated by thermal desorption spectroscopy (TDS). Desorption of Zn was mainly observed from the films deposited at low O2/Ar gas ratio and low RF power. In contrast, O2 desorption was mainly observed from the films deposited at high O2/Ar gas ratio and high RF power. The amount of desorbed O2 from the film increased with increasing the O2/Ar gas flow ratio and the RF power. Furthermore, the desorption temperature of O2 increased with increasing the RF power during the deposition. Thermal stability of the ZnO films was controlled not only by the O2/Ar gas flow ratio, but also applied RF power to the target. 相似文献