全文获取类型
收费全文 | 453篇 |
免费 | 42篇 |
专业分类
化学 | 393篇 |
晶体学 | 7篇 |
力学 | 4篇 |
数学 | 19篇 |
物理学 | 72篇 |
出版年
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 13篇 |
2020年 | 9篇 |
2019年 | 14篇 |
2018年 | 15篇 |
2017年 | 14篇 |
2016年 | 30篇 |
2015年 | 18篇 |
2014年 | 32篇 |
2013年 | 30篇 |
2012年 | 38篇 |
2011年 | 44篇 |
2010年 | 26篇 |
2009年 | 12篇 |
2008年 | 20篇 |
2007年 | 17篇 |
2006年 | 14篇 |
2005年 | 16篇 |
2004年 | 9篇 |
2003年 | 10篇 |
2002年 | 14篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1982年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 4篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1971年 | 1篇 |
1968年 | 2篇 |
1967年 | 4篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1964年 | 1篇 |
1963年 | 2篇 |
1937年 | 2篇 |
排序方式: 共有495条查询结果,搜索用时 0 毫秒
1.
The centrosymmetric title compound, [Cd2{CH3OC6H4P(OC5H9)S2}4], features an eight‐membered [? Cd? S? P? S? ]2 ring owing to the presence of bridging dithiolate ligands. Tetrahedral coordination geometries for cadmium are completed by chelating ligands. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
2.
Toshiaki Asakai Ryota Minegishi Norie Inaba Yutaka Ishimura Mariko Murayama Tatsuhiko Tanaka 《Analytical sciences》2006,22(3):461-463
The drying conditions for primary standards of volumetric analysis have a significant effect on the titration results due to changes in the purity, stability and homogeneity. Amidosulfuric acid, a strong acid used as a reference material for volumetric analysis in Japan, was dried in a vacuum desiccator or heated at different temperatures, and then measured by Karl-Fischer titration, thermogravimetry/mass spectroscopy (TG-MS), ion chromatography and coulometric titration. The optimum drying conditions were at 50 degrees C for 24 h with crushing. 相似文献
3.
4.
The total synthesis of a new platelet aggregation-inhibiting gamma-lactam PI-091 (1) gave a 1:1 diastereomeric mixture at the gamma-ketal carbon. The high-yielding aldol reaction of an appropriately protected 1,3,4-trihydroxy-4-methyldecan-2-one 42, prepared from D-glucose, with the kinetically generated enolate of 3-methyl-2-butanone provided 43. The resulting diastereomeric mixture of the aldol adduct 43 was converted to a 2,4-alkylated furan 45 via an intramolecular ketalization followed by dehydration. The addition of a singlet oxygen to the alpha-trimethylsilylated furan 48derived from 45 under photochemical conditions efficiently provided an alpha,gamma-dialkylated gamma-hydroxy gamma-lactone 47. The transformation of methyl ketal 52 prepared from 47 into gamma-hydroxy gamma-lactam 53 was achieved by exposure to liquid ammonia in MeOH. The total synthesis of 1 was achieved from 52 through the Dess-Martin periodinane oxidation of the secondary hydroxy group in the side chain. The present total synthesis revealed that the stereogenic carbon center in the side chain in natural 1 is S. 相似文献
5.
Shimizu H Tada N Ikawa R Kume T Sasaki S 《The journal of physical chemistry. B》2005,109(47):22285-22289
Visual observations through a microscope and in situ Raman measurements have been made for single crystalline ethylene hydrate (EH) and binary methane-ethylene hydrate (MEH) at pressures up to 3.7 GPa and room temperature. Both hydrates showed pressure-induced phase transitions at 1.6, 2.0, and 3.0 GPa for EH and at 1.7, 2.1, and 3.3 GPa for MEH. The cubic sI phase of EH and MEH remains stable up to 1.6 and 1.7 GPa, respectively, which are more widely ranging values than the values for the methane hydrate sI phase. In this sI phase of binary MEH, the cage occupancies by methane and ethylene molecules are investigated from Raman spectra. Above P = 3.0 GPa for EH and 3.3 GPa for MEH, they decomposed by associating with the formation of the polyethylene. 相似文献
6.
Combination of cyanocobalamin (VB12) and ascorbic acid (VC) has been widely seen in pharmaceutical products and dietary supplements. However, VB12 has been reported that its behavior in stability in aqueous solution is quite different when VC is mixed. In the present study, we examined the stabilities of these vitamins in acetate buffer (pH 4.8) using high performance liquid chromatography. Degradation of VB12 was not observed in the absence of VC in the buffer. However, when VC was mixed in the VB12 solution, VB12 concentrations decreased in accordance with VC degradation. VB12 and VC degradations were inhibited by adding sodium halides to acetate buffer at pH 4.8. These stabilization effects were also observed in the range from pH 3.5 to 5.3 and by adding potassium, magnesium, and calcium halides. Furthermore, our data demonstrated that increases in the halide anion concentrations and atomic number (Cl-相似文献
7.
M Miyauchi K Sasahara K Fujimoto I Kawamoto J Ide H Nakao 《Chemical & pharmaceutical bulletin》1989,37(9):2369-2374
The degradation kinetics of pivaloyloxymethyl (POM) esters of cephalosporins in phosphate buffer solution (pH 6-8) were investigated. The degradation of the starting delta 3 cephalosporin ester proceeded mainly via isomerization to the delta 2 ester and subsequent hydrolysis to the delta 2 acid. Hydrolysis to the delta 3 acid (the parent acid) was very slow. Analysis of the rate constants indicated that the isomerization rate k12 was approximately equal to the apparent degradation rate of the delta 3 ester kdeg, and slower than the hydrolysis rate of the delta 2 ester k24. The isomerization process to the delta 2 ester was found to be the rate-determining step in the degradation of cephalosporin esters. The substituent at the C-3 position of the cephalosporins affected the degradation kinetics. The degradation was accelerated by increase of pH, buffer concentration and added protein. 相似文献
8.
Reactions of allylides () with nitrile oxides () afforded furanylglyoxylate oxime () and 6H-l,2-oxazine (). Ring transformations of and gave and pyrrolinone (), respectively. 相似文献
9.
Nishiyama Y Kaneda M Saito R Mori T Wada T Inoue Y 《Journal of the American Chemical Society》2004,126(21):6568-6569
In the enantiodifferentiating photoaddition of ROH (R = Me, Et, i-Pr) to 1,1-diphenylpropene sensitized by fructosyl 1,4-naphthalenedicarboxylate in supercritical carbon dioxide, the enantiomeric excess of photoadduct increased with increasing bulkiness of the alcohol at all pressures used, with an accompanying sudden jump at the critical density, for which the enhanced clustering of alcohol, particularly in the subcritical pressure region, was revealed to be responsible from the fluorescence spectral examinations. 相似文献
10.
Maki Sachiko Eiji Nishibori Shinobu Aoyagi Makoto Sakata Masaki Takata Mio Kondo Masaki Murata Ryota Sakamoto Hiroshi Nishihara 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(7):696-703
The title compound, [Fe2(C5H5)2(C40H22O2)] or 1,4‐(FcPh)2Aq [where FcPh is 2‐(4‐ferrocenylphenyl)ethynyl and Aq is anthraquinone], was synthesized in an attempt to obtain a new solvent‐incorporating porous material with a large void space. Thermodynamic data for 1,4‐(FcPh)2Aq show a phase transition at approximately 430 K. The crystal structure of solvent‐free 1,4‐(FcPh)2Aq was determined at temperatures of 90, 300 and 500 K using synchrotron powder diffraction data. A direct‐space method using a genetic algorithm was employed for structure solution. Charge densities calculated from observed structure factors by the maximum entropy method were employed for model improvement. The final models were obtained through multistage Rietveld refinements. In both phases, the structures of which differ only subtly, the planar Aq fragments are stacked alternately in opposite orientations, forming a one‐dimensional column. The FcPh arms lie between the stacks and fill the remaining space, leaving no voids. C—H...π interactions between the Ph and Fc fragments mediate crystal packing and stabilization. 相似文献