全文获取类型
收费全文 | 1270篇 |
免费 | 122篇 |
国内免费 | 91篇 |
专业分类
化学 | 985篇 |
晶体学 | 13篇 |
力学 | 36篇 |
综合类 | 4篇 |
数学 | 168篇 |
物理学 | 277篇 |
出版年
2023年 | 22篇 |
2022年 | 21篇 |
2021年 | 32篇 |
2020年 | 36篇 |
2019年 | 49篇 |
2018年 | 39篇 |
2017年 | 35篇 |
2016年 | 51篇 |
2015年 | 51篇 |
2014年 | 47篇 |
2013年 | 67篇 |
2012年 | 102篇 |
2011年 | 86篇 |
2010年 | 74篇 |
2009年 | 54篇 |
2008年 | 74篇 |
2007年 | 62篇 |
2006年 | 65篇 |
2005年 | 67篇 |
2004年 | 52篇 |
2003年 | 39篇 |
2002年 | 61篇 |
2001年 | 59篇 |
2000年 | 39篇 |
1999年 | 33篇 |
1998年 | 14篇 |
1997年 | 19篇 |
1996年 | 25篇 |
1995年 | 15篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1992年 | 12篇 |
1991年 | 12篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 1篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1483条查询结果,搜索用时 296 毫秒
41.
TaoJIANG BuXingHAN GuoYingZHAO ZhongHaoLI YanHongCHANG HaiXiangGAO JunChunLI 《中国化学快报》2004,15(3):296-299
The oxidation of styrene with molecular oxygen catalyzed by PdCl2 CuCl2 has been investigated in supercritical CO2 with a batch reactor. The oxidative system of styrene contains four components at the beginning and seven components during the reaction. The critical temperature, critical pressure, and critical density at different conversions are determined by using a high-pressure view cell. The effect of phase behavior on the conversion and selectivity were studied. Experimental results showed that the critical parameters of the reaction mixture at fixed initial molar ratio changed with the conversion of reactant. The conversion of styrene reached maximum near the critical density of the reaction mixture. Product selectivity also varied with density of reaction mixture and could be tuned to some degree. 相似文献
42.
微量稀土对超导稳定化基体铜材的性能和组织的影响 总被引:4,自引:0,他引:4
研究了微量稀土元素对铜的机械性能、导电性和组织的影响,在铜中加入微量钇、钕、镝、铒和富铈混合稀土后,使铜的抗拉强度有所提高,并保持良好的塑性和导电性。 相似文献
43.
The reactions of 1,4-bis(phenylthio)butane (L) with Ag(I) salts in varied conditions (varying the solvents, metal-to-ligand ratios, and counteranions) lead to the formation of four new two-dimensional (2D) coordination polymers with different network structures: [Ag(2)L(3)(ClO(4))(2)](infinity) 1, [Ag(2)L(3)(ClO(4))(2) x CH(3)OH](infinity) 2, [[AgL(2)](ClO(4))](infinity) 3, and [AgLNO(3)](infinity) 4. All the structures were established by single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P-1, a = 11.0253(9) A, b = 11.3455(9) A, c = 11.5231(9) A, alpha = 93.931(2) degrees, beta = 92.689(2) degrees, gamma = 112.9810(10) degrees, Z = 2. 2: triclinic, P-1, a = 11.9147(13) A, b = 16.1534(17) A, c = 16.2259(17) A, alpha = 74.977(2) degrees, beta = 69.030(2) degrees, gamma = 69.986(2) degrees, Z = 2. 3: triclinic, P-1, a = 12.1617(9) A, b = 12.5054(10) A, c = 13.1547(10) A, alpha = 64.3370(10) degrees, beta =85.938 (2) degrees, gamma = 69.3010(10) degrees, Z = 2. 4: monoclinic, P2(1)/c, a = 5.4032(17) A, b = 16.974(6) A, c = 19.489(6) A, beta = 94.234(6) degrees, Z = 4. In all four complexes, each Ag(I) center has a tetracoordination geometry, and the 2D networks consist of fused large macrometallacyclic ring systems. The "hexagonal" 42-membered rings, Ag(6)L(6), observed in 1 and 2 are nearly identical, which could be considered as unique examples of self-sustaining noninterpenetrated frameworks formed with flexible ligands. The repeating rectangular 28-membered macrometallacycle, Ag(4)L(4), is the basis for the network of 3, in which the perchlorate anions occupy the voids to prevent the ring from collapsing. In 4, columns of the fused rectangular 22-membered rings, Ag(4)L(2)(NO(3))(2), are cross-linked through the L ligands to form a unique 2D network consisting of two types of 22-membered repeating units. 相似文献
44.
K. Przybylski T. Brylewski M. Bućko 《Journal of Thermal Analysis and Calorimetry》1995,45(5):1099-1108
Calcination conditions of the precursor powders, i.e. temperature, type of atmosphere and duration, were determined with a view to obtain superconducting powders with the most advantageous physico-chemical properties. Investigated were powders in the Y?Ba?Cu?O system prepared by the sol-gel method. Thermogravimetric examinations of the powders have revealed that the decomposition kinetics of BaCO3 determines the formation rate of the superconducting YBa2Cu3O7?x (‘123’) phase. It follows from the decomposition kinetics of BaCO3 that the process is the most intensive in argon, whereas in static air and oxygen it is the slowest. The phase composition analysis (XRD) and low-temperature magnetic susceptibility measurements of the calcinated powders, confirm the above mentioned changes in the decomposition kinetics. The reaction of barium carbonate can be completed if the calcination process is conducted at the temperature of 850°C for 25 h, yielding easily sinterable powders for obtaining single-phase superconducting bulk samples with advantageous functional parameters. 相似文献
45.
Geometry optimizations are performed at the DFTB3LYP6-311+G* level. Four intriguing coupling modes, totally eight stable structures are found in the potential energy surfaces of the water-assisted coupling of imidazole dimer radical cation. In these isomers, the water molecules are embedded between two imidazole moieties, and the oxygen atom is tridentate or quadridentate, respectively. The distinct redshifts of the vibrational frequencies of the O-H...N and N-H...O type H bonds indicate the strong interaction of two imidazole rings of respective isomer. Inspection of the highest occupied molecular orbital predicts the alterations of the geometry structures on oxidation and reduction. The low barrier of the fragment rotation demonstrates that the isomerization processes by experiencing the distinct transition states are easy to fulfill, especially for those with O-H...N and C-H...O H bonds. Both the energy difference of the 0 degrees-cis and 180 degrees-trans orientation and the barriers of the fragment rotation are lowered by the water assisting. The range of the zero point vibrational energy correction indicates that the influence on the complexes with N-H...O and O-H...N H bonds (0.13-0.17 kcal/mol) is more significant than those with O-H...N and C-H...O H bonds (+/-0.03 kcal/mol). The dissociation energies of these isomers indicate that the charges transfer easily through water in the dissociation process and then are distributed mainly over the imidazole ring connecting with water molecule. The isomer with proton transfer between imidazole fragments is the most stable one. 相似文献
46.
用 p H法在 (2 5.0± 0 .1 )℃ ,I=0 .1 mol· dm-3 KNO3 条件下 ,测定 Cu( ) - 4 - (喹啉 - 8′-甲基 ) - 1 ,4,7,1 0 -四氮杂环十三烷 - 1 1 ,1 3-二酮 -α-氨基酸或 5-取代邻菲罗啉两类三元配合物的稳定常数 ;研究了带甲基喹啉侧基大环多胺配体与 Cu( )离子的配位能力、配位方式 ;发现这两类三元体系配合物有特殊的稳定性 ;而且它们的稳定性与配体α-氨基酸及 5-取代邻菲罗啉酸碱强度之间的直线自由能关系的变化趋势相反 ;探讨了 Cu( )和 5-取代邻菲罗啉之间的 d- p反馈π键及其取代基 Hammett诱导效应的关系。 相似文献
47.
A hydrated sodium indium sulfide, Na5(In4S)(InS4)3.6H2O, has been prepared by hydrothermal synthesis. This material contains a tetrahedral sulfur site coordinated to four trivalent indium ions, an unusual bonding pattern not previously observed in open framework chalcogenides. The structure is related to the perovskite (CaTiO3) type with simultaneous substitutions of Ti by SIn4, O by InS4, and Ca2+ by [Na5(H2O)6]5+. It is a wide-gap semiconductor and shows photocatalytic activity under UV light for hydrogen generation from aqueous solution without use of any cocatalyst. 相似文献
48.
N. S. Prostakov Hanna Bu Habib V. A. Rezakov A. A. Fomichev L. M. Kirillova V. K. Shevtsov 《Chemistry of Heterocyclic Compounds》1984,20(8):911-915
It was established that the side product that is formed in substantial amounts in the phenylation of -picoline by phenyllithium is 3-methyl-2-phenyl-5-(3-methyl-2-phenyl-3,4-dehydropiperidyl-6)pyridine — a structural analog of anabasine. Its structure was demonstrated by spectral methods and by chemical conversions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 115–119, August, 1984. 相似文献
49.
从光干涉方式,瞳窗关系和光源带宽等基本关系出发,利用空间不变系统理论解析了相移显微干涉检测系统中衍射效应的影响。为了减小横向分辨率对纵向分辨率的影响,利用相关信息提取或数字滤波的方法,获得了纳米分辨率的三维形貌。 相似文献
50.
The surfactant-encapsulated cluster (SEC) composed of a hydrophobic dimethyl dioctadecyl ammonium (DODA) shell and an encapsulated hydrophilic polyoxoanion core can form casting films. The structure of the casting film is influenced by evaporation rates of organic solvent. When the casting films are prepared by slow evaporation of chloroform, the alkyl chains are considered to possess a partial interdigitation, and the interdigitated length is 1.6 nm. The casting film structure is characterized by scanning force microscopy (SFM), Fourier transformation infrared (FT-IR), wide-angle X-ray diffraction, and differential scanning calorimetry (DSC). 相似文献