全文获取类型
收费全文 | 7408篇 |
免费 | 186篇 |
国内免费 | 25篇 |
专业分类
化学 | 5441篇 |
晶体学 | 92篇 |
力学 | 100篇 |
综合类 | 1篇 |
数学 | 358篇 |
物理学 | 1627篇 |
出版年
2022年 | 44篇 |
2021年 | 72篇 |
2020年 | 82篇 |
2019年 | 88篇 |
2018年 | 56篇 |
2017年 | 54篇 |
2016年 | 113篇 |
2015年 | 116篇 |
2014年 | 131篇 |
2013年 | 335篇 |
2012年 | 313篇 |
2011年 | 379篇 |
2010年 | 186篇 |
2009年 | 214篇 |
2008年 | 380篇 |
2007年 | 383篇 |
2006年 | 396篇 |
2005年 | 403篇 |
2004年 | 383篇 |
2003年 | 270篇 |
2002年 | 284篇 |
2001年 | 209篇 |
2000年 | 206篇 |
1999年 | 116篇 |
1998年 | 67篇 |
1997年 | 76篇 |
1996年 | 107篇 |
1995年 | 80篇 |
1994年 | 98篇 |
1993年 | 105篇 |
1992年 | 114篇 |
1991年 | 108篇 |
1990年 | 84篇 |
1989年 | 96篇 |
1988年 | 90篇 |
1987年 | 70篇 |
1986年 | 69篇 |
1985年 | 127篇 |
1984年 | 127篇 |
1983年 | 72篇 |
1982年 | 93篇 |
1981年 | 82篇 |
1980年 | 78篇 |
1979年 | 84篇 |
1978年 | 76篇 |
1977年 | 88篇 |
1976年 | 67篇 |
1975年 | 55篇 |
1974年 | 53篇 |
1973年 | 67篇 |
排序方式: 共有7619条查询结果,搜索用时 15 毫秒
81.
Koudai Tanaka 《Tetrahedron letters》2004,45(42):7859-7861
Reaction of δ-silyl-γ,δ-epoxy-α,β-unsaturated acylsilanes with KCN in the presence of chloro or cyanoformates gives highly functionalized dienol silyl ether derivatives via a twofold Brook rearrangement-induced tandem sequence. 相似文献
82.
M. Toba S. Tanaka S. Niwa F. Mizukami Z. Koppány L. Guczi 《Journal of Sol-Gel Science and Technology》1998,13(1-3):1037-1041
In order to achieve functional group selective hydrogenation, the layer structure of Ru-Sn-Al2O3 catalysts was controlled by using sol-gel, powder impregnation and combined sol-gel impregnation methods. The properties of the catalysts and effectiveness in hydrogenation of dimethyl terephthalate were examined. The surface Sn contents of the catalysts characterized by X-ray photoelectron spectroscopy depended on the preparation method, in spite of almost the same bulk Ru and Sn compositions measured by X-ray fluorescence analyses. TPR and CO adsorption of the catalysts also depended on the preparation method. With regard to the conversion rate of dimethyl terephthalate and the rate of product conversion from methyl 4-hydroxy methylbenzoate to p-xylene via methyl p-toluate, Ru impregnation catalysts had higher rates than the other catalysts. 相似文献
83.
Kiyotake Suenaga Tsuyoshi Mutou Takashi Itoh Noboru Takada Masaki Takagi Hideo Kigoshi Kiyoyuki Yamada 《Tetrahedron》2004,60(38):8509-8527
The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S3 cells with an IC50 of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1. 相似文献
84.
Hiromi Matsuhashi Masakazu Oikawa Hiromi Shibata Michiko Tanaka 《Reaction Kinetics and Catalysis Letters》1998,65(2):253-258
Reversible formation of F+-centers was observed over platinum promoted sulfated zirconia in the presence and absence of hydrogen. The intensity of ESR
signal of F+-centers was increased by treatment in He stream and it was decreased rapidly by supply of hydrogen in gas phase. This behavior
seems to be related to proton spillover. 相似文献
85.
Kenji Yokota Hideo Tomioka Teruyuki Ono Fumimasa Kuno 《Journal of polymer science. Part A, Polymer chemistry》1972,10(5):1335-1343
The sensitization effect of tertiary amines on the photopolymerization of methyl methacrylate was studied. N,N-Dimethylbenzylamine, triethylamine, and N,N-dimethylaniline increased the rate of polymerization in this order, but pyridine did not show any effect. A free-radical mechanism was confirmed by the tacticity of polymer, the retarding effect of hydroquinone, and the copolymer composition with styrene. On the basis of the detailed kinetics of the sensitized polymerization and the ultraviolet spectra of the reaction mixtures, a sensitization mechanism is proposed, in which the excited monomer and the amine form a complex and generate an initiating radical. 相似文献
86.
To detect a lectin from soybean, an electrochemical procedure was developed by the use of a labeling of galactosamine. Because the lectin has binding sites to galactosamine, galactosamine labeled with daunomycin having electroactivity was prepared. When labeled galactosamine (LG) combines with lectin, the part of daunomycin is taken in the binding sites of the lectin and becomes electroinactive. Therefore, the concentration of the lectin can be estimated by measuring the peak current of the LG. On the other hand, a competitive reaction to the lectin of galactosamine and the LG makes a detection of galactosamine possible. This method has merit that does not require a separation procedure of the free LG from the bound one. An effect of length of spacer between daunomycin and galactosamine was also investigated. It was found that adsorption of reagent on the electrode increased due to introduction of the spacer. Furthermore, the electrode response of the LG was influenced by the type of the spacer. 相似文献
87.
M. Takeuchi S. Tanaka M. Yamawaki S. Tachimori 《Journal of Radioanalytical and Nuclear Chemistry》1995,191(1):189-199
The coextraction equilibrium of technetium(VII) and uranium(VI) from nictric acid solution was studied in a system involvingn-octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) in decalin. Stoichiometry of technetium, uranium and CMPO in the Tc-U-CMPO complex was obtained from the distribution data by slope analysis. The results indicated that the enhanced extraction of technetium was caused by the formation of UO2NO3TcO4·nCMPO (wheren=2 and/or 3). It was found that this coextraction of technetium with uranium was well explained by using ion exchange reaction between UO2(NO3)2·2CMPO complex and TcO
4
–
. 相似文献
88.
K. Komura K. Komura Y. Kuwahara Y. Kuwahara T. Abe T. Abe K. Tanaka K. Tanaka Y. Murata Y. Murata M. Inoue M. Inoue 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(2):511-516
Summary Extremely low activity levels of cosmic ray induced nuclides have been measured in freshly precipitated rainwater by quick
chemical separation coupled with ultra low background gamma-spectrometry. The nuclides detected were 38S (T1/2 = 2.83 h)-38Cl (37.2 m), 39Cl (55.6 m), 24Na (14.96 h), 28Mg (20.9 h), 7Be (53.3 d) and 22Na (2.602 y). The number of atoms in rain water were evaluated to be ranging from 400-1900 l-1 for 39Cl (n = 6, mean: 1200), 30-1500 l-1 for 24Na (n = 16, mean: 520), 80-600 l-1 for 28Mg (n = 13, mean: 260), 1 . 106-4 . 107 l-1 for 7Be (n = 16, mean: 7 . 106) and 2 . 103-1 . 105 l-1 for 22Na (n = 9, mean: 2 . 104). Measurements of activity levels and activity ratios of short-lived cosmic-ray induced short-lived nuclides will open new
method to understand atmospheric processes occurred at the altitude of rain cloud. 相似文献
89.
The enantio-controlled synthesis of trans-4,5-benzhydrindan-1-ones was achieved by means of a stereoselective [4+2] cycloaddition of o-quinodimethanes generated by a thermal cleavage of benzocyclobutene derivatives as a key step. The chiral substrates of the thermal reaction were synthesized by a diastereoselective Grignard addition to the chiral O-isopropylideneglyceroketones connected to a benzocyclobutene ring, which were simply prepared from D-mannitol as a chiral source. This approach can provide a new efficient access to A-nor B-aromatic steroidal compounds. 相似文献
90.
Ikedou K Yamamoto H Nagashima H Nemoto N Tashiro K 《The journal of physical chemistry. B》2005,109(21):10668-10675
We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches. 相似文献