全文获取类型
收费全文 | 346篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 295篇 |
晶体学 | 1篇 |
力学 | 1篇 |
数学 | 12篇 |
物理学 | 47篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 6篇 |
2019年 | 4篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 4篇 |
2015年 | 7篇 |
2014年 | 11篇 |
2013年 | 21篇 |
2012年 | 27篇 |
2011年 | 34篇 |
2010年 | 18篇 |
2009年 | 9篇 |
2008年 | 30篇 |
2007年 | 30篇 |
2006年 | 22篇 |
2005年 | 22篇 |
2004年 | 19篇 |
2003年 | 20篇 |
2002年 | 25篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 4篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1978年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有356条查询结果,搜索用时 15 毫秒
1.
2.
Komatsu H Iwasawa N Citterio D Suzuki Y Kubota T Tokuno K Kitamura Y Oka K Suzuki K 《Journal of the American Chemical Society》2004,126(50):16353-16360
The role of intracellular magnesium ions is of high interest in the fields of pharmacology and cellular biology. To accomplish the dynamic and three-dimensional imaging of intracellular Mg2+, there is a strong desire for the development of optimized Mg2+ fluorescent probes. In this paper we describe the design, synthesis, and cellular application of the three novel Mg2+ fluorescent probes KMG-101, -103, and -104. The compounds of this series feature a charged beta-diketone as a binding site specific for Mg2+ and a fluorescein residue as the fluorophore that can be excited with an Ar+ laser such as is widely used in confocal scanning microscopy. This molecular design leads to an intensive off-on-type fluorescent response toward Mg2+ ions. The two fluorescent probes KMG-103 and -104 showed suitable dissociation constants (Kd,Mg2+ = 2 mM) and nearly a 10-fold fluorescence enhancement over the intracellular magnesium ion concentration range (0.1-6 mM), allowing high-contrast, sensitive, and selective Mg2+ measurements. For intracellular applications, the membrane-permeable probe KMG-104AM was synthesized and successfully incorporated into PC12 cells. Upon application of the mitochondria uncoupler FCCP to the probe-incorporated cells, the resulting increase in the free magnesium ion concentration could be followed over time. By using a confocal microscope, the intracellular 3D magnesium ion concentration distributions were satisfactorily observed. 相似文献
3.
A microanalytical method for the determination of traces of natural brassinosteroids as their dansylaminophenylboronates by liquid chromatography with fluorimetric detection is described. The boronates are easily prepared by the reaction of brassinosteroids with dansylaminophenylboronic acid (DABA), which was newly synthesized as a precolumn fluorogenic reagent for brassinosteroids. The potential of the method is demonstrated by the separation of a standard brassinosteroid mixture and the analysis of a biologically active fraction sample obtained from an extract of Zea mays L. pollen. The detection limit of the DABA derivative was found to be 25 pg for brassinolide, which is superior to that of the phenanthreneboronate derivative. 相似文献
4.
Masanari KimuraRyutaro Mukai Naoko TanigawaShuji Tanaka Yoshinao Tamaru 《Tetrahedron》2003,59(39):7767-7777
Without prior activation of allyl alcohols, allylation of a variety of active methylene compounds with allyl alcohols proceeds smoothly at rt-50°C in the presence of catalytic amounts of Pd(OAc)2 (1-10 mol%), Et3B (30-240 mol%), a phosphine ligand (1-20 mol%), and a base (0 to 50-60 mol%). 相似文献
5.
Nabeshima T Tsukada N Nishijima K Ohshiro H Yano Y 《The Journal of organic chemistry》1996,61(13):4342-4350
Synthesis and metal binding properties of thiolariat ethers, where a sulfide side chain is introduced into a framework of a crown ether, have been performed. Remarkably high Ag(+) selectivity among heavy metal ions was observed in solvent extraction and transport across a liquid membrane using thiolariat ethers with a 15-crown-5 ring as carriers. Thiolariat ethers with a 12-crown-4 or a 18-crown-6 do not exhibit such a high Ag(+) selectivity. The former binds metal ions weakly, and the latter recognizes Pb(2+) as well as Ag(+). The corresponding oxygen analogs, i.e. lariat ethers, do not show Ag(+) selectivity. The Ag(+) binding strength of the sulfoxide and sulfone analogs is much lower than that of thiolariat ethers. Thiolariat ethers with a benzocrown framework containing a sulfide chain at the 4 position of the benzene nucleus showed very low affinity to Ag(+). Extractability and transport ability using various thiolariat ether derivatives strongly suggested that this high Ag(+) selectivity is a result of the synergistic coordination of the ring oxygen and the sulfur atom of the thiolariat ether. NMR chemical shifts of protons and carbons in the proximity of the sulfur atom of the thiolariat ether were changed significantly in accordance with the synergistic coordination described above. 1:1 Complexation between a thiolariat ether and Ag(+) were supported by a Job plot using the chemical shift of the methylene protons adjacent to the sulfur atom. 相似文献
6.
Akiko Tsuhako Jing-Qian He Mariko Mihara Naoko Saino Sentaro Okamoto 《Tetrahedron letters》2007,48(52):9120-9123
Ketones and aldehydes were effectively reduced to the corresponding alcohols (or their silyl ethers) by the reaction with CaH2 and R3SiCl in the presence of a catalytic amount of ZnCl2. In the absence of the carbonyl substrate, the reagent reduced R3SiCl to the corresponding hydrosilane under mild reaction conditions. 相似文献
7.
The lipase-catalyzed transesterifications of various substituted diphenyl 1,2-ketals of glycerol have been investigated. Efficient modification of the substrate structure with bis(4-bromophenyl) ketal was found to enhance the enantioselectivity up to E=57 at 0 °C. 相似文献
8.
Tsuda M Izui N Shimbo K Sato M Fukushi E Kawabata J Katsumata K Horiguchi T Kobayashi J 《The Journal of organic chemistry》2003,68(13):5339-5345
A novel cytotoxic 16-membered macrodiolide, amphidinolide X (1), has been isolated from a marine dinoflagellate Amphidinium sp. (strain Y-42). The gross structure of 1 was elucidated on the basis of spectroscopic data including one-bond and long-range (13)C-(13)C correlations. The relative and absolute stereochemistries were determined by combined analyses of NOESY data and (1)H-(1)H and (1)H-(13)C coupling constants of 1 and NMR data of the degradation products. Amphidinolide X (1) is the first macrodiolide consisting of polyketide-derived diacid and diol units from natural sources. The biosynthetic origins of 1 were investigated by means of feeding experiments with (13)C-labeled acetates. 相似文献
9.
Size, shape, and flexibility of micelles of octaoxyethylene tetradecyl C(14)E(8), hexadecyl C(16)E(8), and octadecyl C(18)E(8) ethers in dilute aqueous solutions were determined at finite surfactant concentrations c by static light scattering (SLS) and dynamic light scattering experiments at several temperatures T below the critical points. The SLS results were successfully analyzed with the aid of the thermodynamic theory formulated with wormlike spherocylinder model for SLS of micelle solutions. The analysis yielded the molar mass M(w) of the micelles as a function of c and the cross-sectional diameter d. The hydrodynamic radius R(H) and the radius of gyration S(2)(1/2) of the micelles as functions of M(w) were found to be also well-described by the corresponding theories for the wormlike spherocylinder or wormlike chain models. The results of the stiffness parameter lambda(-1) have revealed that the micelles are far from rigid rods but rather stiff compared with typical flexible polymers and they grow in size with increasing T to greater length for longer hydrophobic chains, i.e., alkyl groups of the surfactants. As the alkyl group becomes longer, the d value increased, while the spacings s between adjacent hexaoxyethylene chains on the micellar surface were found to remain substantially constant. 相似文献
10.
Imai M Tanaka M Tanaka K Yamamoto Y Imai-Ogata N Shimowatari M Nagumo S Kawahara N Suemune H 《The Journal of organic chemistry》2004,69(4):1144-1150
Intermolecular hydroacylation between salicylaldehydes 1, 26-40 and 1,4-penta- or 1,5-hexadienes 4-13 by Rh-catalyst proceeded under mild reaction conditions to give a mixture of iso- and normal-hydroacylated products 14-25, 41-55, and 57-60. In the hydroacylation reaction, chelation of both salicylaldehyde and diene to the Rh-complex plays a crucial role. The ratio of iso- and normal-hydroacylated products could be regulated by the addition of salicylic acid or amines. The effects of various Rh-complexes, solvents, and additives were examined, and the plausible mechanisms of the catalytic cycle were proposed on the basis of the deuterium-labeling salicylaldehyde experiments. 相似文献