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31.
Acid-catalyzed oligomerization of 2-(hydroxymethyl)pyrroles bearing C6F5, 2,6-Cl2C6H3, CF3 and CO2Et groups at beta-positions was examined. The reaction of ethyl pyrrole-3-carboxylates gave a mixture of oligomers and type I isomers of porphyrinogens and hexaphyrinogens were isolated when the other beta-substituents were sufficiently bulky, for example, mesityl, 2,6-Cl2C6H3 and C6F5 groups. On the other hand, the pyrroles having other electron-withdrawing groups afforded porphyrinogens as the only isolable products. 相似文献
32.
The electrophoretic detection of two kinds of p-quinone anion radicals arising from the electrolysis of benzoquinone and chloranil was achieved by employing an acetonitrile medium. Sufficient dehydration of a running solution was necessary for the detection of the benzoquinone anion radical. Oxygen in the running solution also caused a serious decrease in the amount of the benzoquinone anion radical during electrophoresis. The addition of methanol as a hydrogen-donor decreased the electrophoretic mobility of the benzoquinone anion radical significantly, while that of the chloranil anion radical was little changed. This result is interpreted in terms of hydrogen-bonding interaction between the p-quinone anion radicals and methanol, reflecting the magnitude of their proton-accepting ability (benzoquinone anion radical > chloranil anion radical). 相似文献
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34.
Hiroki Uoyama Kil Suk Kim Dr. Kenji Kuroki Jae‐Yoon Shin Dr. Toshi Nagata Dr. Tetsuo Okujima Dr. Hiroko Yamada Dr. Noboru Ono Prof. Dongho Kim Prof. Hidemitsu Uno Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(13):4063-4074
Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ(2)) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways. 相似文献
35.
Naotake Nakamura Kenjiro Uno Yoshihiro Ogawa 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(11):1389-1390
In the molecular structure of the title compound, C21H44O2, the hydrocarbon skeleton has an all‐trans conformation. One of the terminal hydroxyl groups is also trans with respect to the skeleton, while the other is gauche. In the crystal structure, the molecules lie parallel to the b axis, forming layers with a thickness of b/2. The packing is similar to that in the smectic A phase of liquid crystals. These features are similar to those of the homologues with an odd number of C atoms, but different from those with an even number. 相似文献
36.
Takahiro Nakae Ryuji Ohnishi Yoshiharu Kitahata Tatsuya Soukawa Hisako Sato Shigeki Mori Tetsuo Okujima Hidemitsu Uno Hiroshi Sakaguchi 《Tetrahedron letters》2012,53(13):1617-1619
6,13-Diiododibenzo[a,h]anthracene and 5,8-diiodopicene were synthesized by AuCl-catalyzed double cyclization. The highly selective reaction yielded a new class of peri-halogenated fused aromatics. 相似文献
37.
Michael Widhalm Michael Abraham Vladimir B. Arion Siret Saarsalu Uno Maeorg 《Tetrahedron: Asymmetry》2010,21(16):1971-1982
A group of five phosphino hydrazones with a pendant binaphthyl unit as a chiral modifier has been synthesized from non-racemic 2,2′-bis(bromomethyl)-1,1′-binaphthyl and 3,3′-diiodo-2,2′-bis(bromomethyl)-1,1′-binaphthyl as the key intermediates. Their efficiency as chiral ligands in palladium-catalyzed allylic alkylation reactions has been investigated showing up to 95% ee under optimized conditions. X-ray diffraction structures of mono- and dimeric Pd complexes are also reported. 相似文献
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39.
Kenji Tamura Hikaru Uno Hirohisa Yamada Kiyoshi Umeyama 《Journal of Polymer Science.Polymer Physics》2009,47(6):583-595
The effect of two different species of layered silicates on the morphology, mechanical properties, and methanol vapor barrier properties of polyamide‐6 (PA6) nanocomposites was examined using identical experimental conditions for both species. The layered silicate species used were natural montmorillonite (MMT) and synthetic expandable fluoro‐mica (FM), the chemical compositions of which were Na0.43(Al1.56Mg0.31Fe2+ 0.09)(Si3.95Al0.05)O10(OH)2 and Na0.66Mg2.68(Si3.98Al0.02)O10F2, respectively. The layered silicates were modified with a dodecylammonium salt (DDA) using an ion‐exchange method. The resulting organically modified layered silicates were melt‐kneaded with PA6 in a twin‐screw kneader at 260 °C. By quantitative analysis of the silicate layers dispersed in the PA6, the number‐average aspect ratio was estimated to be 76 for DDAMMT‐PA6 and 85 for DDAFM‐PA6. This confirmed that the primary particle size of the initial silicate did affect the aspect ratio. The rigidity and gas barrier properties of the nanocomposites appeared to depend upon the morphology of the nanocomposite. On the other hand, the elongation at break of the nanocomposites decreased as the amount of silicate increased. This reduction in ductility was ascribed to the difference in morphology of the nanocomposites, that is, distribution of silicate nanolayers in the polymer matrix. The homogeneity of the particle fraction of exfoliated nanolayers was clearly an important factor affecting the properties of the nanocomposites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 583–595, 2009 相似文献
40.
The metabolites 3 and 4 of 2-(4-ethyl-1-piperazinyl)-4-phenylquinoline dimaleate (AS-2646, 1), a candidate as a gastric antisecretory and antiulcer drug, were synthesized to confirm the proposed structures. The effects of the metabolites 2-4 on ulcer induced by stress were determined. 相似文献