全文获取类型
收费全文 | 837篇 |
免费 | 11篇 |
专业分类
化学 | 624篇 |
晶体学 | 6篇 |
力学 | 9篇 |
数学 | 7篇 |
物理学 | 202篇 |
出版年
2023年 | 5篇 |
2021年 | 4篇 |
2020年 | 8篇 |
2019年 | 10篇 |
2016年 | 5篇 |
2015年 | 12篇 |
2014年 | 18篇 |
2013年 | 32篇 |
2012年 | 40篇 |
2011年 | 39篇 |
2010年 | 15篇 |
2009年 | 27篇 |
2008年 | 57篇 |
2007年 | 48篇 |
2006年 | 49篇 |
2005年 | 40篇 |
2004年 | 37篇 |
2003年 | 23篇 |
2002年 | 34篇 |
2001年 | 19篇 |
2000年 | 17篇 |
1999年 | 7篇 |
1998年 | 9篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 7篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 13篇 |
1991年 | 13篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 16篇 |
1987年 | 22篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 7篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 10篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 11篇 |
1975年 | 5篇 |
1974年 | 9篇 |
1973年 | 11篇 |
1970年 | 4篇 |
1966年 | 4篇 |
排序方式: 共有848条查询结果,搜索用时 62 毫秒
1.
Y Sonoda K Ichinose T Yoshimura Y Sato T Sasaki 《Chemical & pharmaceutical bulletin》1991,39(1):100-103
Lanosterol derivatives with a functional group at C-32 have been synthesized from 3 beta-acetoxylanostan-7 alpha-ol. The key reaction of the synthesis is the hypoiodite reaction of 3 beta-acetoxylanostan-7 alpha-ol. In vitro antitumor activity testing of the lanosterol derivatives revealed that 3 beta-hydroxylanost-7-en-32-oic acid has antineoplastic activity. 相似文献
2.
S. B. Ellis S. J. Kiehl W. S. Hughes K. Schwabe W. C. Gardiner H. L. Sanders H. Yoshimura Hanna Jablezynska-Jedrzewska J. Domański W. A. Dorfman P. Nylén Barbara Stone F. Hovorka W. C. Dearing E. Biilmann W. Kordatzki P. Wulff G. Florence A. Drilhon P. Szigeti O. Tomiček F. Poupě O. Redlich W. Stricks 《Analytical and bioanalytical chemistry》1937,111(2-4):94-104
3.
Etsuro Yoshimura Mariko Akashi Tomonari Umemura Kin-ichi Tsunoda 《Analytical sciences》2004,20(2):373-374
27Al NMR spectra of an equimolar (10 mM) Al(III)-citrate system were obtained at different temperatures. The linewidths of the signals decreased in the spectra recorded at elevated temperatures, which enabled us to unequivocally identify the resonance lines. From the spectrum recorded at 65 approximately C, a mononuclear Al(III)-citrate complex was identified at a solution pH of 3.0 in addition to trinuclear Al(III)-citrate complex, which dominated at pH 4.0. 相似文献
4.
5.
Masaaki Kubota Raul A. Reimer Kuniko Terajima Yuji Yoshimura Akio Nishijima 《Analytica chimica acta》1987
Inductively-coupled plasma/atomic emission spectrometry with a high-resolution vacuum scanning monochromator is described for the determination of sulfur at 180.734 nm. The behavior of the signal-to-background ratio is investigated as functions of RF power, argon gas flow rate and observation height above the load coil. Under the operating conditions selected, the detection limit is 3 μg l?1. The Se I 196.090-nm line is chosen as internal standard, because the S/Se line pair exhibited the least change with carrier gas flow rate and acid concentration of solution. Sulfur in NiMo and CoMo/ Al2O3 catalysts used for coal liquefaction is determined as S(II) and S(VI) species. The total amount of the species agreed well with the sulfur value obtained by the conventinal combustion method. 相似文献
6.
7.
Interactions between poly(amidoamine) dendrimer (PAMAM)-gold nanocomposites and alkanethiols and between the former nanocomposites and thiol-modified poly(amidoamine) dendrons in ethyl acetate were investigated by adding alkanethiols, such as 1-propanethiol and 1,3-propanedithiol, and thiol-modified poly(amidoamine) dendrons, generations 0.5 and 2.5 (G0.5-SH and G2.5-SH). The PAMAM dendrimers with surface methyl ester groups used were generations 1.5 and 5.5 (G1.5 and G5.5). The mean particle sizes of PAMAM-gold nanocomposites were about 2.1 for G1.5 and 2.4 nm for G5.5. In both nanocomposite systems where 1-propanethiol and 1,3-propanedithiol were added, the mean particle size was about 4 nm, twice that of the systems where these thiols were not added. Increasing the addition of 1,3-propanedithiol made the average particle size smaller for both nanocomposites systems. To compare with alkanethiol, thiol-modified poly(amidoamine) dendron with a highly branched structure on one side was synthesized. Using G2.5-SH as a protective agent, dendron-gold nanocomposites with mean diameters of 3 to 4 nm were obtained. The difference in particle size was seen only when the combination of PAMAM-gold nanocomposites and thiol-modified dendron was less sterically dense, modified dendron (G0.5-SH). The mechanisms for morphology changes in the dendrimer-gold nanocomposites by the addition of these thiols are discussed. 相似文献
8.
Kunihito Miyake Yasuhiro Masaki Ikuya Miyamoto Shozo Yanagida Takeshi Ohno Akio Yoshimura Chyongjin Pac 《Photochemistry and photobiology》1993,58(5):631-636
We have investigated the photosensitized monomerization of the cis,syn -cyclobutane dimer of 1,3-di-methylthymine using riboflavin tetraacetate and a 5-deazaflavin derivative as photosensitizer. Although little monomerization of the dimer is induced by photoexcitation of the flavins in the absence of any additives, the flavins can function as an efficient photosensitizer in the presence of magnesium perchlorate. Mechanistic studies involving spectroscopic, quantum-yield and flash-photolysis measurements demonstrated that the photosensitized monomerization exclusively proceeds through electron transfer from the dimer to the triplet flavins complexed with Mg2+ . The effects of magnesium perchlorate are compared with those on the chloranil-photosensitized monomerization and also with the effects of HClO4 on the flavin-photosensitized reaction. 相似文献
9.
Optically active o-substituted diphenyl N-substituted sulphilimines are readily synthesised by the reaction of the corresponding sulphides and t-butyl hypochlorite in the presence of l-menthol and amide anions. (−)-N-p-Tolylsulphonylsulphilimines (1, 2) obtained were converted to the corresponding (−)-N-unsubstituted sulphilimines (8, 9) by treating them with concentrated sulphuric acid. When (−)-S-o-anisyl S-phenyl N-(unsubstituted) sulphilimine (8) was treated with acylating agents or acrylonitrile, the corresponding optically active (−)-N-substituted sulphilimines were prepared with complete retention at sulphur. The absolute configuration of (−)-S-o-anisyl S-phenyl N-p-tolylsulphonylsulphilimine (1) was determined by converting it to (+)-S-o-anisyl sulphoxide (17). CD curves of (−)-o-substituted diarylsulphilimines exhibited a negative Cotton effect at around 270–285 nm, which was assigned to (S)-configuration at sulphur by comparing with the analogous sulphoxides. The substituent on the imino group of the sulphilimine gave no appreciable effect on the CD behavior and the lack of substituent effect was considered to be due to the semi-polar character of the S(IV)-N bond. Unusual effect of o-methoxy group on the CD curves was discussed in connection with solvent effect. Mechanism of this asymmetric synthesis has been investigated, and it has become apparent that the diastereomeric menthoxysulphonium chloride was an excess of (RR)-configuration was formed initially and the amide anion attacks the S atom of the salt with net inversion. 相似文献
10.
Temperature dependence of ion and water transport in perfluorinated ionomer membranes for fuel cells
To clarify the mechanisms of transport of ions and water molecules in perfluorosulfonated ionomer membranes for fuel cells, the temperature dependence of their transport behaviors was investigated in detail. Two types of Flemion membranes having different equivalent weight values (EW) were utilized along with Nafion 117 as the perfluorinated ionomer membranes, and H-, Li-, and Na-form samples were prepared for each membrane by immersion in 0.03 M HCl, LiCl, and NaCl aqueous solutions, respectively. The ionic conductivity, water self-diffusion coefficient (D(H)(2)(O)), and DSC were measured in the fully hydrated state as a function of temperature. The ionic conductivity of the membranes was reflected by the cation transport through the intermediary of water. Clearly, H(+) transports by the Grotthuss (hopping) mechanism, and Li(+) and Na(+) transport by the vehicle mechanism. The differences of the ion transport mechanisms were observed in the activation energies through the Arrhenius plots. The D(H)(2)(O) in the membranes exhibited a tendency similar to the ionic conductivity for the cation species and the EW value. However, no remarkable difference of D(H)(2)(O) between H- and the other cation-form membranes was observed as compared with the ionic conductivity. It indicates that water in each membrane diffuses almost in a similar way; however, H(+) transports by the Grotthuss mechanism so that conductivity of H(+) is much higher than that of the other cations. Moreover, the D(H)(2)(O) and DSC curves showed that a part of water in the membranes freezes around -20 degrees C, but the nonfreezing water remains and diffuses below that temperature. This fact suggests that completely free water (bulk water) does not exist in the membranes, and water weakly interacting with the cation species and the sulfonic acid groups in secondary and higher hydration shells freezes around -20 degrees C, while strongly binding water in primary hydration shells does not freeze. The ratio of freezing and nonfreezing water was estimated from the DSC curves. The D(H)(2)(O) in the membranes was found to be influenced by the ratio of freezing and nonfreezing water. DFT calculation of the interaction (solvation) energy between the cation species and water molecules suggested that the water content and the ratio of freezing and nonfreezing water depend strongly on the cation species penetrated into the membrane. 相似文献