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61.
Dysidiolide (1), a novel sesterterpenoid previously isolated from the Caribbean sponge Dysidea etheria de Laubenfels, inhibits the action of the protein phosphatase, cdc25A. The authors establish a novel total synthesis of natural dysidiolide (1) using intramolecular Diels-Alder reaction as the key step from optically active cyclohexenone 3. Decalin, the core structure of 1, was constructed by intramolecular Diels-Alder reaction of the diene ester generated by elimination of the phenyl sulfoxide group from sulfoxide ester 6 prepared from cyclohexenone 3. Diastereoselective methylation at C-7, alkylation at C-6, and deoxygenation of C-12 and C-24 positions gave the fully substituted bicyclic core of 1. The two side chains of the bicyclic core were further extended so as to afford natural dysidiolide (1). The total yield of this synthesis exceeds that of previous syntheses of 1. 相似文献
62.
M Kajiwara K Kurumaya Y Kohno K Tomita A T Carpenter 《Chemical & pharmaceutical bulletin》1989,37(12):3386-3389
The oxidation of tyrosine by monophenol monooxygenase (tyrosinase: EC 1.10.3.1) to melanin has been studied by a combination of ultraviolet, circular dichroism, and nuclear magnetic resonance techniques. It is demonstrated that the chiral intermediate (dopachrome) is generated stereoselectively in this enzymic reaction. 相似文献
63.
Hideo Sawada Tamikazu Narumi Atsushi Kajiwara Katsuya Ueno Kazuo Hamazaki 《Colloid and polymer science》2006,284(5):551-555
Fluoroalkyl end-capped oligomers reacted with tetraethoxysilane and silica/nanoparticles under alkaline conditions to afford
fluoroalkyl end-capped oligomers/silica nanoparticles (mean diameters: 31–54 nm) with a good dispersibility and stability
in organic media. Interestingly, the isolated fluorinated particle powders were found to afford nanometer size-controlled
colloidal particles with a good redispersibility and stability in these media. In addition, fluoroalkyl end-capped oligomers/silica
nanoparticles-encapsulated guest molecules such as stable organic radicals and ionic liquids were prepared under similar conditions.
These fluorinated nanoparticles-encapsulated guest molecules were applied to a new type of surface-modification agent, and
these particles were able to disperse well above the poly (methyl methacrylate) films. 相似文献
64.
Norihiro Tokitoh Hiroyuki Suzuki Nobuhiro Takeda Takashi Kajiwara Takahiro Sasamori Renji Okazaki 《Silicon Chemistry》2002,1(5-6):313-319
In this paper, we present the reaction of an overcrowded silylene bearing a 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) group with pivalonitrile and t-butylphosphaalkyne to give the corresponding [1+2] cycloadducts, 2H-azasilirene and 2H-phosphasilirene derivatives. This is the first exampleof the isolation of a stable 2H-azasilirene derivative, and the X-ray crystallographic analysis unambiguously revealed its three-membered ring structure in the solid state. In addition, DFT calculations supported three-membered ring character in the structures of the 2H-azasilirene and 2H-phosphasilirene. 相似文献
65.
Propagating radicals could be transformed into corresponding cations in the radical polymerization process of vinyl monomers in the presence of an electron acceptor. The electron transfer reaction from the propagating radicals to the acceptor was confirmed by an electron spin resonance study and by the model compound reaction. The radical/cation transformation polymerization was effectively applied to the preparation of a new type of block copolymer compound of radically polymerized segments and cationically polymerized segments by the one shot method. Thus, a block copolymer of p-methoxystyrene (MOS) and cyclohexene oxide (CHO) was prepared by the radical polymerization of MOS in the presence of Ph2I+PF−6 and CHO. The formation of the block copolymer was confirmed by extraction separation, 1H-NMR (nuclear magnetic resonance), thin layer chromatography and turbidimetric titration. © 1997 John Wiley & Sons, Ltd. 相似文献
66.
Mitsuru Mimura Hiroshi Urakawa Kanji Kajiwara Shinichi Kitamura Kenichi Takeo 《Macromolecular Symposia》1995,99(1):43-55
(1→4)-α- and (1→4)-β-D-linked glucosidic oligosaccharide chains were generated by the Monte Carlo method, and the scattering from the systems composed of simulated chains was calculated to compare with the results of small-angle X-ray scattering from the oligosaccharides in aqueous solution. By extending the simulation to a longer chain, a single chain conformation of (1→4)-α- and (1→4)-β-D-linked polysaccharides was evaluated. On the basis of the simulation, the suprastructure of (1→4)-α- and (1→4)-β-D-linked polysaccharides and their gel formation mechanism were discussed in some detail by analyzing the small-angle X-ray scattering from the aqueous solutions of (1→4)-α- and (1→4)-β-D-linked polysaccharides. 相似文献
67.
68.
Hexakis(4-(4'-heptyloxy)biphenoxy)cyclotriphosphazene (HHCP) was synthesized from hexachlorocyclotriphosphazene and 4-heptyloxy-4'-hydroxybiphenyl. The mesogenicity of HHCP was studied by DSC, FTIR spectroscopy and polarizing microscopy. Enantiotropic smectic C and nematic phases were observed between 450 and 455 K and 455 and 456 K, respectively, on heating, and between 456 and 455 K (nematic) and 455 and 440 K (smectic C) on cooling from the isotropic liquid phase. The introduction of the heptyloxybiphenoxy groups as side chains into cyclotriphosphazene has generated the liquid crystalline phase. FTIR spectroscopy showed that the P=N and P-O-(C) stretching vibrations converted to lower frequencies from 1224 to 1210 cm-1 and from 920 to 910cm-1, respectively, at the crystalline (C)-Sc phase transition. This result suggests that the state of the cyclotriphosphazene ring dramatically changes near the C-Sc phase transition. 相似文献
69.
70.
Taihei Mukaide Satoshi Mogi Jun Yamamoto Akira Morita Shinnosuke Koji Kazuhiro Takada Kentaro Uesugi Kentaro Kajiwara Takashi Noma 《Journal of synchrotron radiation》2008,15(4):329-334
In situ visualization of the distribution and behaviour of water in a polymer electrolyte fuel cell during power generation has been demonstrated using a synchrotron X‐ray imaging technique. Images were recorded using a CCD detector combined with a scintillator (Gd2O2S:Tb) and relay lens system, which were placed at 2.0 m or 2.5 m from the fuel cell. The images were measured continuously before and during power generation, and data on cell performance was recorded. The change of water distribution during power generation was obtained from X‐ray images normalized with the initial state of the fuel cell. Compared with other techniques for visualizing the water in fuel cells, this technique enables the water distribution and behaviour in the fuel cell to be visualized during power generation with high spatial resolution. In particular, the effects of the specifications of the gas diffusion layer on the cathode side of the fuel cell on the distribution of water were efficiently identified. This is a very powerful technique for investigating the mechanism of water flow within the fuel cell and the relationship between water behaviour and cell performance. 相似文献