全文获取类型
收费全文 | 1101篇 |
免费 | 25篇 |
国内免费 | 14篇 |
专业分类
化学 | 873篇 |
晶体学 | 7篇 |
力学 | 8篇 |
数学 | 76篇 |
物理学 | 176篇 |
出版年
2022年 | 4篇 |
2021年 | 4篇 |
2020年 | 17篇 |
2019年 | 13篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 19篇 |
2015年 | 20篇 |
2014年 | 34篇 |
2013年 | 82篇 |
2012年 | 50篇 |
2011年 | 64篇 |
2010年 | 27篇 |
2009年 | 37篇 |
2008年 | 62篇 |
2007年 | 61篇 |
2006年 | 74篇 |
2005年 | 53篇 |
2004年 | 59篇 |
2003年 | 50篇 |
2002年 | 35篇 |
2001年 | 27篇 |
2000年 | 31篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 17篇 |
1996年 | 9篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 6篇 |
1992年 | 10篇 |
1991年 | 16篇 |
1990年 | 18篇 |
1989年 | 16篇 |
1988年 | 17篇 |
1987年 | 12篇 |
1986年 | 4篇 |
1985年 | 15篇 |
1984年 | 16篇 |
1983年 | 8篇 |
1982年 | 19篇 |
1981年 | 12篇 |
1980年 | 10篇 |
1979年 | 7篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1974年 | 5篇 |
1973年 | 7篇 |
1968年 | 3篇 |
1966年 | 4篇 |
排序方式: 共有1140条查询结果,搜索用时 10 毫秒
151.
152.
153.
Cho J Furutachi H Fujinami S Tosha T Ohtsu H Ikeda O Suzuki A Nomura M Uruga T Tanida H Kawai T Tanaka K Kitagawa T Suzuki M 《Inorganic chemistry》2006,45(7):2873-2885
The reaction of [Ni2(OH)2(Me2-tpa)2]2+ (1) (Me2-tpa = bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) with H2O2 causes oxidation of a methylene group on the Me2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(III) ([Ni2(O)2(Me2-tpa)2]2+ (2)), a bis(mu-superoxo)dinickel(II) ([Ni2(O2)2(Me2-tpa)2]2+ (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni2(OH)(Me2-tpa)(Me-tpa-CH2OO)]2+ (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni2(Me-tpa-CH2OO)2]2+ (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) and a ligand-coupling dimer (Me-tpa-CH2)2. The formation of (Me-tpa-CH2)2 suggests that a ligand-based radical Me-tpa-CH2* is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2* is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence of O2 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)2, indicating that the reaction of Me-tpa-CH2* with O2 is faster than the coupling of Me-tpa-CH2* to generate ligand-based peroxyl radical Me-tpa-CH2OO*. Although there is a possibility that the Me-tpa-CH2OO* species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the aldehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction. 相似文献
154.
1-Chlorovinyl p-tolyl sulfoxides were synthesized from ketones and chloromethyl p-tolyl sulfoxide in high yields. Treatment of the sulfoxides with isopropylmagnesium chloride at −78 °C in toluene gave magnesium alkylidene carbenoids (α-chloro alkenylmagnesium chlorides), which were treated with N-lithio arylamines to afford ortho-alkenylated arylamines in moderate yields. The reaction, in some cases, proceeded in a highly stereospecific manner at the carbon bearing the chlorine and the sulfinyl group. The structures of the α-chloro alkenylmagnesium chlorides and the reactivity of the N-lithio meta-substituted anilines were studied at the B3LYP and MP2 levels of theory with the 6-31(+)G* basis set. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic ring. 相似文献
155.
The effect of MCM-41 on the ESR spectrum of an aqueous spin probe solution was observed. The sharp ESR spectrum turns into a rather broad characteristic one leaving a sharper signal as the minor component, immediately after the addition of MCM-41 powder to the system. This observation indicates that MCM-41 traps the solute molecule into the nanochannel by letting the solvent water form a rather stable molecular cage, since the ESR line shape indicates that the nitroxide radical undergoes anisotropic rotation without being adsorbed on the wall. Thermodynamic parameters for this process are estimated from the temperature dependencies of the trapping efficiency. This process is explained in terms of the surface enthalpy of the liquid specifically intensified in the nanospace. 相似文献
156.
We have investigated aggregation phenomena in a polydisperse colloidal dispersion of ferromagnetic particles simulated by employing the cluster-moving Monte Carlo method in an applied magnetic field. The influence of both particle-particle and particle-field interactions on the aggregate structures is analyzed in terms of a pair correlation function. The results obtained in this study are summarized as follows: Under a strong magnetic field, chainlike clusters are formed along the magnetic field direction, and they become thickly clustered with an increase in the strength of the external magnetic field. Moreover, the thickly clustered chains are formed for a polydisperse system that has a large standard deviation of particle diameters. In contrast, for a very weak magnetic field, the strong interaction between the larger particles gives rise to the formation of various shapes in the chainlike clusters, including bending, looping, and branching. With an increase in the external magnetic field, these structures reorganize to form straight chainlike clusters. Furthermore, the thickness of the chainlike clusters for the polydisperse system is found to depend on the standard deviation of the particle-size distribution but is found to be independent of the magnetic field strength. 相似文献
157.
Nakayama M Tanaka A Sato Y Tonosaki T Ogura K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(13):5907-5913
Manganese and molybdenum mixed oxides in a thin film form were deposited anodically on a platinum substrate by cycling the electrode potential between 0 and +1.0 V vs Ag/AgCl in aqueous manganese(II) solutions containing molybdate anion (MoO(4)2-). A possible mechanism for the film formation is as follows. First, electrooxidation of Mn2+ ions with H2O yields Mn oxide and protons. Then, the protons being accumulated near the electrode surface react with MoO(4)2- to form polyoxomolybdate through a dehydrated condensation reaction (by protonation and dehydration). The condensed product coprecipitates with the Mn oxide. Cyclic voltammetry of the Mn/Mo oxide film-coated electrode in aqueous 0.5 M Na2SO4 solution exhibited a pseudocapacitive behavior with higher capacitance and better rate capability than that of the pure Mn oxide prepared similarly, most likely as a result of an increase in electrical conductivity of the film. Electrochemical quartz crystal microbalance and X-ray photoelectron spectroscopy clearly demonstrated that the observed pseudocapacitive behavior results from reversible extraction/insertion of hydrated protons to balance the charge upon oxidation/reduction of Mn3+/Mn4+ in the film. 相似文献
158.
[reaction: see text]. An In(OTf)(3)-catalyzed addition of a beta-ketoester to acetylene in the presence of molecular sieves produces a alpha-vinylated ketoester in good to excellent yield. The vinylation reaction proceeds without any loss of elements in starting molecules under solvent-free conditions and allows the use of welding-grade acetylene, providing a practical method for synthetic utilization of acetylene gas. 相似文献
159.
The size distribution of new vesicles formed after addition of oleate in different forms to preformed egg yolk phosphatidylcholine (EggPC) vesicles was studied by gel exclusion chromatography. The addition of oleate to preformed vesicles resulted in the formation of new small vesicles. Fission of preformed vesicles incorporated by oleate and partial solubilization of the vesicles by addition of oleate in micellar form were involved in the process of the new small vesicle formation. 相似文献
160.
Iida T Satoh H Maeda K Yamamoto Y Asakawa K Sawada N Wada T Kadowaki C Itoh T Mase T Weissman SA Tschaen D Krska S Volante RP 《The Journal of organic chemistry》2005,70(23):9222-9229
[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1. 相似文献