全文获取类型
收费全文 | 1626篇 |
免费 | 44篇 |
国内免费 | 3篇 |
专业分类
化学 | 1342篇 |
晶体学 | 10篇 |
力学 | 7篇 |
数学 | 17篇 |
物理学 | 297篇 |
出版年
2022年 | 7篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 25篇 |
2018年 | 12篇 |
2017年 | 11篇 |
2016年 | 22篇 |
2015年 | 20篇 |
2014年 | 41篇 |
2013年 | 72篇 |
2012年 | 80篇 |
2011年 | 96篇 |
2010年 | 49篇 |
2009年 | 43篇 |
2008年 | 81篇 |
2007年 | 74篇 |
2006年 | 76篇 |
2005年 | 97篇 |
2004年 | 75篇 |
2003年 | 61篇 |
2002年 | 43篇 |
2001年 | 63篇 |
2000年 | 60篇 |
1999年 | 35篇 |
1998年 | 26篇 |
1997年 | 33篇 |
1996年 | 25篇 |
1995年 | 20篇 |
1994年 | 31篇 |
1993年 | 32篇 |
1992年 | 39篇 |
1991年 | 25篇 |
1990年 | 20篇 |
1989年 | 24篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 10篇 |
1985年 | 25篇 |
1984年 | 27篇 |
1983年 | 25篇 |
1982年 | 12篇 |
1981年 | 16篇 |
1980年 | 15篇 |
1979年 | 21篇 |
1978年 | 13篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1971年 | 4篇 |
排序方式: 共有1673条查询结果,搜索用时 15 毫秒
21.
Kazuhiro Endo Hideo Ihara Kazuhiro Watanabe Shun-Ichi Gonda 《Journal of solid state chemistry》1982,44(2):268-272
X-Ray photoelectron spectra of TiS3 with a one-dimensional structure were measured. TiS3 may be regarded as Ti4+(S2)2?S2? with pairs of S atoms (S2) and isolated S atoms. The spectra of the sulfur core-levels are assigned by comparison with those of TiS2, where all S atoms are largely separated. The binding energy of the S2 pairs is found to be 1.4 eV higher than that of the isolated S atoms, which is consistent with the larger negative charge of the isolated atoms. The structures of the valence band of TiS3 are discussed in terms of a molecular orbital scheme for the S2 pairs. 相似文献
22.
Ohmiya H Tsuji T Yorimitsu H Oshima K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5640-5648
Details of cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic Grignard reagents are disclosed. A combination of cobalt(II) chloride and 1,2-bis(diphenylphosphino)ethane (DPPE) or 1,3-bis(diphenylphosphino)propane (DPPP) is suitable as a precatalyst and allows secondary and tertiary alkyl halides--as well as primary ones--to be employed as coupling partners for allyl Grignard reagents. The reaction offers a facile synthesis of quaternary carbon centers, which has practically never been possible with palladium, nickel, and copper catalysts. Benzyl, methallyl, and crotyl Grignard reagents can all couple with alkyl halides. The benzylation definitely requires DPPE or DPPP as a ligand. The reaction mechanism should include the generation of an alkyl radical from the parent alkyl halide. The mechanism can be interpreted in terms of a tandem radical cyclization/cross-coupling reaction. In addition, serendipitous tandem radical cyclization/cyclopropanation/carbonyl allylation of 5-alkoxy-6-halo-4-oxa-1-hexene derivatives is also described. The intermediacy of a carbon-centered radical results in the loss of the original stereochemistry of the parent alkyl halides, creating the potential for asymmetric cross-coupling of racemic alkyl halides. 相似文献
23.
Yohei Hashimoto Masataka Moriyasu Eiko Kato Masaru Endo Naohiko Miyamoto Hiroshi Uchida 《Mikrochimica acta》1978,70(1-2):159-167
Summary A new type of detector for high-pressure liquid chromatography has been designed. This detector is equipped with a RC resonance circuit, and is similar to the capacitance detector previously reported. It is operated as a capacitance detector with nonpolar eluents; while with polar solvents, it behaves as a conductance detector. Electrolytes such as salts, acids and bases are sensitively detected. The detector was successfully used for the detection of fatty acids and alkaloids.
Zusammenfassung Ein neuartiger Detektor für die Hochdruck-Flüssigchromatographie wurde entwickelt. Dieser ist mit einem Resonanzstromkreis ausgestattet und ähnelt dem kürzlich beschriebenen Kapazitanz-Detektor. Als solcher funktioniert er mit nichtpolaren Eluenten, während er sich mit polaren Lösungsmitteln wie ein Leitfähigkeitsdetektor verhält. Salze, Säuren und Basen werden empfindlich nachgewiesen. Das Gerät wurde zum Nachweis von Fettsäuren und Alkaloiden verwendet.相似文献
24.
Akihiko Kanazawa Tomiki Ikeda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1993,31(2):335-343
Various polymeric phosphonium salts and the corresponding low-molecular-weight model compounds were prepared and their antibacterial activities against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method in sterile distilled water. Antibacterial activity of the polymers was found to be higher than that of the corresponding model compounds, particularly against S. aureus. Furthermore, the polymeric phosphonium salt exhibited a higher activity by 2 orders of magnitude than the polymeric quaternary ammonium salt with the same structure except the cationic part. Compounds with the longest alkyl chain (octyl) studied were found to exhibit particularly high activity, and this finding may be ascribed to the contribution of the increased hydrophobicity of the compounds to the cidal activity. © 1993 John Wiley & Sons, Inc. 相似文献
25.
Hitomi Uno Toshikazu Takata Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1989,27(5):1675-1685
Graft copolymerization of a bicycloorthoester (BOE) with polymer-supported sulfonium salts was studied. Several polymer-supported sulfonium salts were prepared by the homopolymerizations of p-vinylbenzyl tetramethylenesulfonium hexafluoroantimonate ( 2 ) and 4-(p-vinylphenyl)butyl tetramethylenesulfonium hexafluoroantimonate ( 3 ), and by the copolymerizations of 2 with some vinyl monomers (n-butyl vinyl ether, styrene, acrylonitrile, and p-styrenesulfonic acid potassium salt). These sulfonium salts could initiate the polymerization of BOE to give grafted polymers. Temperature dependences of the catalytic activity of them were not so dramatic as that of benzyl tetramethylenesulfonium hexafluoroantimonate ( 1 ), but the activities of them were higher than that of 1 at temperatures lower than 80°C. The conversion of BOE in the polymerizations with these polymer initiators was ca. 30–70% at 120°C for 7 h. An effect of the comonomer structure on the catalytic activity was observed and styrene was the best comonomer for 2 in terms of the reactivity of the copolymer. The spacer-modified sulfonium salt (homopolymer of 3 ) was slightly lower than polymer-supported benzyl type sulfonium salt (homopolymer of 2 ) in the catalytic activity. 相似文献
26.
Doi H Sakai T Iguchi M Yamada K Tomioka K 《Journal of the American Chemical Society》2003,125(10):2886-2887
The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities. 相似文献
27.
T. Kobayashi I. Endo A. Fukumi T. Horiguchi Y. Ishida T. Kondo T. Kuwamoto N. Minamoto T. Nakamura T. Takahasi 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,39(3):209-216
Atomic-beam laser spectroscopy with fluorescence detection is applied to investigate the hyperfine structure (hfs), Stark and Zeeman effects of the electric dipole transitions of Sm i. The measurements are performed for the four transitions of 0 → 15650.55, 292.58 → 15650.55, 292.58 → 15567.32, and 1489.55 → 16890.59 cm-1. The hfs constants of the upper and lower levels and the isotope shifts of the transitions are determined. The tensor polarizability of the 15650.55 cm-1 level is found to be α2 = -556.2 ± 11.8 kHz/(kV/cm)2. Thanks to the accurate g values of the lower levels [Childs, W.J., Goodman, L.S.: Phys. Rev. A 6, 2011 (1972)], the g values of the upper levels are obtained from the observed Zeeman splittings. The values are found to be -0.115907(79), 2.22259(20) and 1.599968(51) for the 15650.55 cm-1 .1, 15567.32 cm-1 and 16890.59.cm-1 levels, respectively. 相似文献
28.
Takeo Miyazawa Takeshi Endo Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1985,23(5):1527-1535
Some hindered amine polymers containing 2,2,6,6-tetramethylpiperidine structure were synthesized. A new monomer, 4-O-vinylbenzyl-2,2,6,6-tetramethylpiperidine, was homopolymerized and copolymerized with some vinyl monomers in the presence of AIBN as an initiator. The obtained amine polymers were oxidized with hydrogen peroxide to obtain the polymers having nitroxyl radical moiety. 相似文献
29.
Immobilized lectin columns: useful tools for the fractionation and structural analysis of oligosaccharides. 总被引:5,自引:0,他引:5
Elucidation of the binding specificity of a concanavalin A-Sepharose column led to the possibility of the affinity chromatography of oligosaccharides and glycopeptides with the use of immobilized lectin columns. Subsequent addition of immobilized erythroagglutinating phytohaemagglutinin, Aleuria aurantia lectin, Datura stramonium agglutinin, Ricinus communis agglutinin and Allomyrina dichotoma agglutinin to the range of well characterized lectin columns has afforded a way to fractionate a mixture of N-linked oligosaccharides even to a single component. 相似文献
30.
[reaction: see text]. An In(OTf)(3)-catalyzed addition of a beta-ketoester to acetylene in the presence of molecular sieves produces a alpha-vinylated ketoester in good to excellent yield. The vinylation reaction proceeds without any loss of elements in starting molecules under solvent-free conditions and allows the use of welding-grade acetylene, providing a practical method for synthetic utilization of acetylene gas. 相似文献