全文获取类型
收费全文 | 1108篇 |
免费 | 25篇 |
国内免费 | 4篇 |
专业分类
化学 | 674篇 |
晶体学 | 16篇 |
力学 | 56篇 |
数学 | 174篇 |
物理学 | 217篇 |
出版年
2022年 | 25篇 |
2021年 | 23篇 |
2020年 | 14篇 |
2019年 | 15篇 |
2018年 | 15篇 |
2017年 | 10篇 |
2016年 | 35篇 |
2015年 | 25篇 |
2014年 | 34篇 |
2013年 | 78篇 |
2012年 | 57篇 |
2011年 | 72篇 |
2010年 | 36篇 |
2009年 | 38篇 |
2008年 | 63篇 |
2007年 | 60篇 |
2006年 | 57篇 |
2005年 | 49篇 |
2004年 | 35篇 |
2003年 | 28篇 |
2002年 | 30篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 8篇 |
1998年 | 15篇 |
1997年 | 12篇 |
1996年 | 18篇 |
1995年 | 14篇 |
1994年 | 22篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 13篇 |
1990年 | 12篇 |
1989年 | 12篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1981年 | 9篇 |
1980年 | 18篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1976年 | 7篇 |
1975年 | 9篇 |
1974年 | 6篇 |
1972年 | 6篇 |
1968年 | 6篇 |
1966年 | 5篇 |
排序方式: 共有1137条查询结果,搜索用时 515 毫秒
31.
Arturo Battaglia Eleonora Baldelli Gabriele Fontana Andrea Guerrini 《Tetrahedron》2005,61(32):7727-7745
The base induced deprotonation of H-14 of 7-triethylsilyl- (7-TES-) and 7-tert-butoxycarbonyl- (7-BOC-) protected 13-oxo-baccatins gave the corresponding enolates, which were selectively aminated with electrophilic nitrogen donors, such as azodicarboxylates and tosyl azide. In particular, tosyl azide gave the corresponding 7-BOC- and 7-TES-13-oxo-14β-azido-baccatin III. Alternatively, the last compound was prepared via NaN3 induced azidation of the 13-silyl enol ether of 7-TES-13-oxo-baccatin III under oxidative (cerium ammonium nitrate) conditions. The 13-silyl enol ether was obtained in a multistep process by DBU induced silylation of 7-TES-13-oxo-baccatin III. The 7-TES-13-oxo-14β-azido-baccatin III was used as a key intermediate for the synthesis of a new family of antitumour taxanes containing amino based functional groups at the C-14 position, such as: 14β-azido, 14β-amino, 14β-amino 1, 14-carbamate, 14β-amino 1, 14-thiocarbamate, and 14β-amino N-tert-butoxycarbonyl-1,14-carbamate. 相似文献
32.
Stable polyacrylamide (polyAA)–montmorillonite adducts were prepared by two distinct processes: (1) free radical copolymerization of AA with alkaline clay previously treated with 2-(N-methyl-N,N-diethyl ammonium iodide)ethylacrylate (QD1) and (2) direct interactions of alkaline montmorillonite with various preformed copolymers of AA with QD1. The structure of the adducts as determined by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction was shown to consist of AA macromolecules inserted between lamellar layers whose spacing was larger than in the polymer-free clay. The polymer was strongly attached to the inorganic surfaces, probably due to cooperative formation of electrostatic bonding. The thermal stability of the organic polymers in the resulting complexes was substantially enhanced while the mobility of macromolecules decreased. 相似文献
33.
Reaction of 1-oxo-2-formyl-3-dimethylamino-1H-naphtho[2,1-b]pyran with amidines, guanidine, O-methylisourea, S-methylisothiourea afforded 9-substituted 12-oxo-12H-naphtho[1′,2′:5,6]pyrano[2,3-d]pyrimidines. When the reaction with O-methylisourea was carried out in anhydrous pyridine, 10,20-dioxo-10H,20H-dinaphtho[1,2-e:1′,2′-e′][1,5]diazocino[2,3-b:6,7-b′]dipyran was formed. 相似文献
34.
Cristina Rota Lino Liverani Franco Spelta Giuseppe Mascellani Aldo Tomasi Anna Iannone 《Research on Chemical Intermediates》2006,32(1):73-81
The use of low-molecular-weight heparins (LMWHs) has become common, since compared to unfractionated heparin (UFH), they have
a much longer plasma half-life and lower incidence of side effects. LMWHs are derived from the depolymerization of UFH, obtained
either chemically, physically or enzymatically. We employed electron spin resonance (ESR) spectroscopy to study the depolymerization
of UFH by copper in the presence of hydrogen peroxide. A stable nitroxide radical was detected. This could be generated by
the hydroxyl radical attack either to the N-SO−3 group or to free amino groups present in the UFH preparation. 相似文献
35.
E. Fontana E. Pianezzola G. Basileo M.Strolin Benedetti 《Journal of chromatography. A》1994,660(1-2):293-298
A sensitive and selective high-performance liquid chromatographic method for the determination of FCE 24928 (4-amino-androsta-1,4,6-triene-3, 17-dione) in human plasma is reported. The drug was extracted from buffered (pH = 8) plasma samples with methylene chloride-isooctane, then analysed by reversed-phase liquid chromatography. Quantitation was achieved by ultraviolet detection of the eluate at 238 nm. Blank plasma samples from humans, dog and rat assayed as described showed no significant peak at the retention time of the compound of interest. The suitability of the method for in vivo samples was tested by measuring the plasma levels of FCE 24928 in rats that received oral doses of the test compound. 相似文献
36.
Fontana José D. Almeida Eduardo R. A. Baron Madalena Guimaraes Manoel F. Deschamps Francisco C. Schwartsmann Gllberto Cervi Armando C. Zanette Flávio Vilegas Janete LanÇas Fernando M. 《Applied biochemistry and biotechnology》1994,(1):295-313
The acetogenins are strongly bioactive natural compounds present in the bark, roots, leaves, and seeds of manyAnnonaceae plants. They are modified fatty acids and their cytotoxicities have been determined for different biological models including
the in vitro growth inhibition of several human cancer cell lines.
Very low acetogenin yield (< 0.1 g%) has been found previously in native phytobiomass, and we have now investigated the nonpredatory
exploitation of the seeds as acetogenin sources characterizing the seed triacylglycerols (dominant fraction; > 90% of the
whole lipid extracts) as potential valuable by-products. 相似文献
37.
Migani A Gentili PL Negri F Olivucci M Romani A Favaro G Becker RS 《The journal of physical chemistry. A》2005,109(39):8684-8692
The efficiency of the photochemical ring-opening of chromenes (or benzopyrans) depends on the vibronic transition selected by the chosen excitation wavelength. In the present work, ab initio CASPT2//CASSCF calculations are used to determine the excited-state ring-opening reaction coordinate for 2H-chromene (C) and 2,2-diethyl-2H-chromene (DEC) and provide an explanation for such an unusual mode-dependent behavior. It is shown that excited-state relaxation and decay occur via a multimodal and barrierless (or nearly barrierless) reaction coordinate. In particular, the relaxation out of the Franck-Condon involves a combination of in-plane skeletal stretching and out-of-plane modes, while the second part of the reaction coordinate is dominated exclusively by a different out-of-plane mode. Population of this last mode is shown to be preparatory with respect to both C-O bond breaking and decay via an S(1)/S(0) conical intersection. The observed mode-dependent ring-opening efficiency is explained by showing that the vibrational mode corresponding to the most efficient vibronic transition has the largest projection onto the out-of-plane mode of the reaction coordinate. To support the computationally derived mechanism, we provide experimental evidence that the photochemical ring-opening reaction of 2,2-dimethyl-7,8-benzo(2H)chromene, that similarly to DEC exhibits a mode-dependent photoreaction, has a low ( approximately 1 kcal mol(-1)) activation energy barrier. 相似文献
38.
S. M. Dal Bosco R. S. Jimenez C. Vignado J. Fontana B. Geraldo F. C. A. Figueiredo D. Mandelli W. A. Carvalho 《Adsorption》2006,12(2):133-146
The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater
control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents,
by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption
process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q
0 parameter, which is related to the sorption capacity, corresponding to 6.3 mg g− 1 for K-10/Cd(II), 4.8 mg g− 1 for K-10/Mn(II), 11.2 mg g− 1 for NT-25/Cd(II) and 6.0 mg g− 1 for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction,
a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process
is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of
inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate
positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of
complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have
shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L− 1 solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent. 相似文献
39.
40.