全文获取类型
收费全文 | 216篇 |
免费 | 5篇 |
专业分类
化学 | 177篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 5篇 |
物理学 | 34篇 |
出版年
2015年 | 4篇 |
2014年 | 3篇 |
2013年 | 18篇 |
2012年 | 6篇 |
2011年 | 5篇 |
2010年 | 4篇 |
2009年 | 3篇 |
2008年 | 4篇 |
2007年 | 8篇 |
2006年 | 8篇 |
2005年 | 14篇 |
2004年 | 7篇 |
2003年 | 3篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1998年 | 2篇 |
1996年 | 2篇 |
1994年 | 2篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 6篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1971年 | 5篇 |
1970年 | 4篇 |
1968年 | 6篇 |
1967年 | 2篇 |
1966年 | 2篇 |
1939年 | 4篇 |
1936年 | 2篇 |
1934年 | 2篇 |
1932年 | 3篇 |
1931年 | 2篇 |
1930年 | 2篇 |
1902年 | 2篇 |
1901年 | 2篇 |
1898年 | 2篇 |
1893年 | 2篇 |
1892年 | 2篇 |
1891年 | 3篇 |
1888年 | 2篇 |
1885年 | 2篇 |
1884年 | 2篇 |
排序方式: 共有221条查询结果,搜索用时 16 毫秒
1.
Further exploration of the scope of our solid-phase method for the synthesis of 3-aminobenzisoxazoles (using the Kaiser oxime resin 1) is described. The effects of base, leaving group, and solvent on the nucleophilic aromatic substitution based resin-loading reaction are discussed. Representative aryloxime intermediates were subjected to a variety of acidic conditions commonly used in protecting group removal to establish the acid stability profile of this linker. Regioselectivity was evaluated with various di- and trifluorobenzonitriles, which gave single benzisoxazole products after loading and cyclorelease reactions. Substituent effects observed in the course of the acid stability and regioselectivity studies suggest that the nitrile plays a critical role in the oxime hydrolysis mechanism. Finally, to establish the compatibility of the aryloxime linker with a variety of useful on-resin synthetic transformations, functionalized substrates were loaded onto resin 1, and carbon-nitrogen, carbon-oxygen, and carbon-carbon bond-forming reactions were successfully executed. 相似文献
2.
Tormos JR Wiley KL Seravalli J Nachon F Masson P Nicolet Y Quinn DM 《Journal of the American Chemical Society》2005,127(42):14538-14539
Secondary beta-deuterium kinetic isotope effects have been measured as a function of substrate concentration for recombinant human butyrylcholinesterase-catalyzed hydrolysis of acetyl-L3-thiocholine (L = 1H or 2H). The isotope effect on V/K is inverse, D3V/K = 0.93 +/- 0.03, which is consistent with conversion of the sp2 hybridized carbonyl carbon of the scissile ester bond of the E + A reactant state to a quasi-tetrahedral structure in the acylation transition state. In contrast, the isotope effect on Vmax under conditions of substrate activation is markedly normal, D3(betaVmax) = 1.29 +/- 0.06, an observation that is consistent with accumulation of a tetrahedral intermediate as the reactant state for catalytic turnover. Generally, tetrahedral intermediates for nonenzymatic ester hydrolyses are high-energy steady-state intermediates. Apparently, butyrylcholinesterase displays an unusual ability to stabilize such intermediates. Hence, the catalytic power of cholinesterases can largely be understood in terms of their ability to stabilize tetrahedral intermediates in the multistep reaction mechanism. 相似文献
3.
Shape-controlled synthesis of metal nanostructures: the case of silver 总被引:19,自引:0,他引:19
The concept of shape-controlled synthesis is discussed by investigating the growth mechanisms for silver nanocubes, nanowires, and nanospheres produced through a polymer-mediated polyol process. Experimental parameters, such as the concentration of AgNO(3) (the precursor to silver), the molar ratio between poly(vinylpyrrolidone) (PVP, the capping agent) and AgNO(3), and the strength of chemical interaction between PVP and various crystallographic planes of silver, were found to determine the crystallinity of seeds (e.g., single crystal versus decahedral multiply twinned particles). In turn, the crystallinity of a seed and the extent of the PVP coverage on the seed were both instrumental in controlling the morphology of final product. The ability to generate silver nanostructures with well-defined morphologies provides a great opportunity to experimentally and systematically study the relationship between their properties and geometric shapes. 相似文献
4.
A facile seven-step sequence was developed from 4′-bromopropiophenone, utilizing a Suzuki-type coupling with an alkene, to give several novel 5-substituted pyrazole derivatives in overall yields of 11-31%. They are potent CB1 antagonists and have binding affinities similar to SR 141716A. Like SR 141716A, they may prove to be clinically useful for the treatment of obesity. 相似文献
5.
6.
7.
8.
9.
The EPR spectra of manganese(II) ions on sulfonated polystyrene cross-linked with either pure meta or pure para divinylbenzene show distinctions indicative of ionic environments of different symmetry. 相似文献
10.
Reactivity ratios for the copolymerization of styrene (r 1) meta-divinylben-zene (r 2–m) and with para-divinylbenzene (r 2–p) have been redetermined under different reaction conditions and with different radioactivity assay techniques. The copolymers were prepared at two conversion levels [0.55 to 3.7% and 2.7 to 7.5% and at 80° (rather than 100°)] with benzoyl peroxide (in place of τ-butylhydroperoxide) initiator. The ionization chamber-vibrating reed electrometer radioactivity assay technique developed for other copolymerization studies was used in place of the direct counting technique previously used for the styrene/divinylbenzene systems. The new values are r 1 = 0.605/r 2-m = 0.88: r 1 = 0.77/r 2-p = 2.08 at 0.55 to 3.7% conversion and r 1 = 1.27; r 2–m = 1.08 at 2.7 to 7.5% conversion. These are not in close agreement with previous values partly because of the difference in conditions of copolymerization (temperature, per cent conversion, initiator) and in the improved analytical precision. Also the high-DVB-content (80%) para copolymer data are not assumed to be invalid and are not omitted (as they were before) from selection of the r 2–p values. 相似文献