全文获取类型
收费全文 | 3295篇 |
免费 | 485篇 |
国内免费 | 172篇 |
专业分类
化学 | 2701篇 |
晶体学 | 29篇 |
力学 | 95篇 |
综合类 | 21篇 |
数学 | 236篇 |
物理学 | 870篇 |
出版年
2024年 | 9篇 |
2023年 | 59篇 |
2022年 | 78篇 |
2021年 | 89篇 |
2020年 | 139篇 |
2019年 | 137篇 |
2018年 | 104篇 |
2017年 | 89篇 |
2016年 | 150篇 |
2015年 | 157篇 |
2014年 | 176篇 |
2013年 | 207篇 |
2012年 | 248篇 |
2011年 | 277篇 |
2010年 | 184篇 |
2009年 | 167篇 |
2008年 | 207篇 |
2007年 | 157篇 |
2006年 | 167篇 |
2005年 | 151篇 |
2004年 | 135篇 |
2003年 | 134篇 |
2002年 | 113篇 |
2001年 | 63篇 |
2000年 | 66篇 |
1999年 | 64篇 |
1998年 | 43篇 |
1997年 | 38篇 |
1996年 | 48篇 |
1995年 | 37篇 |
1994年 | 35篇 |
1993年 | 17篇 |
1992年 | 21篇 |
1991年 | 22篇 |
1990年 | 15篇 |
1989年 | 11篇 |
1988年 | 14篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 12篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 7篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1977年 | 8篇 |
1976年 | 3篇 |
1974年 | 7篇 |
1973年 | 4篇 |
排序方式: 共有3952条查询结果,搜索用时 15 毫秒
101.
102.
Fifteen isomers of [Si,N,C,O]2+ system are obtained at UB3LYP/6-311G(d) and UCCSD(T)/6-311+G(2df) (single-point) levels. The analyses are made for predicting the structures of optimized isomers, while ionic fragments with lower energies are suggested. The calculated results indicate that linear isomer SiNCO2+(2Π) is thermodynamically the most stable species in [Si,N,C,O]2+ system, followed by linear SiOCN2+ (2Π), SiCNO2+ (2Π), and SiC(NO) (2A) with NCO three-membered ring. The order of stability of several kinetically stable isomers is SiNCO2> SiCNO2+ (2Π)>SiOCN2+>SiC(NO)2+>OSiNC2+ (2Π). The obtained results by analyzing the isomerizations and ionic fragment patterns show that the signal peaks of [Si,N,C,O]2+ are attributed to the contribution of linear SiNCO2+ species, which is metastable and can dissociate to the ionic fragments in the mass spectrometry experiments. 相似文献
103.
104.
The direct reaction of iron pentacarbonyl with diethylamidocyclohexadiene gave three isomeric tricarbonyliron complexes, 1, 2 and 3. Only 1 isomerized to give 2 under acidic conditions, whereas 3 remained unchanged. The chemical properties of the tricarbonyl(amidocyclohexadiene)iron complexes differed from those of the tricarbonyl(carboxycyclohexadiene)iron complexes. Complex 3 which underwent no hydride abstraction with triphenylmethyl hexafluorophosphate, has an exo stereochemistry. 相似文献
105.
Interlayer energy transfer between 2,3-naphthol-10-hexadecylaza-15-crown-5(NC16) and N-[1-(9-methoxyanthryl)] decylaza-15-crown-5(A10C) within multilayer Langmuir-Blodgett films has been studied by steady-state fluorescence spectra. The donor and acceptor could be separated precisely by inserting stearic acid (SA) spacers. The efficiency of the energy transfer increases with the decrease in the donor-acceptor distance by a quadratic manner, suggesting the donor excitations are delocalized in the layer. 相似文献
106.
Kai-Ming Chi Hung-Chang Houa Kuo-Hsien Chen Shin-Guang Shyu Yuh-Sheng Wen 《中国化学会会志》1995,42(3):547-554
Copper(I) complexes of general formula (β-diketonate)Cu(7-AcO-NBD), where 7-AcO-NBD = 7-norbornadienyl acetate and β-diketonate = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate (1), 1,1,1-trifluoro-2,4-pentanedionate (2), 2,4-pentanedionate (3), 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate (4), 4,4,4-trifluoro-1-phenyl-1,3-butanedionate (5), were prepared from reactions of CuCl with Na(β-diketonate) in the presence of 7-AcO-NBD. AH compounds were characterized by elemental analyses, 1H, 13C, 19F NMR and IR spectra. Single-crystal strucutre of compound 1 was determined by X-ray diffraction analysis that showed a mononuclear copper species with coordination of a chelating β-diketonate ligand through two oxygen atoms and the 7-AcO-NBD through its C? C double bond and an oxygen atom in the solid state. For compound 1, the crystal data are: triclinic, space group $ {\rm P}\bar 1 $, a= 5.4519(14) Å, b= 11.852(3) Å, c= 13.304(3) Å, α = 74.721(20)° β = 80.220(20)°, γ= 76.848(19)°, Z = 2, RF = 0.060 and Rw = 0.064. Hot-wall chemical vapor deposition experiments revealed that compound 1 is suitable as a precursor for deposition of copper films in the temperature range 170–260 °C. 相似文献
107.
Hon Man Lee Chi Ying Lu Chih Yuan Chen Wen Ling Chen Hung Ching Lin Pei Ling Chiu Pi Yun Cheng 《Tetrahedron》2004,60(27):5807-5825
A series of new ethylene-bridged bis(imidazolium) halides with various N-substitutions were synthesized. Complexation of these imidazolium halides with Pd(OAc)2 produced new Pd(II) ethylene-bridged bis(carbene) complexes. Crystallographic analyses of some of the new imidazolium salts and Pd(II) complexes were determined. Applications of these seven-member palladacycles in Suzuki and Heck coupling reactions produced comparable catalytic activities to those of six-member analogs. 相似文献
108.
109.
Oi-lian Song Guang-zhao Zhang Chi Wu 《高分子科学》2007,(5):441-445
Using a core(142 nm)made of linear polystyrene(PS)chains as a seed,we further polymerized a thin layer of cross-linked PS shell(7 nm)on it in water to form a core-shell particle.Such a particle swells in toluene,which enables linear PS chains inside the core to gradually diffuse out through the porous shell.Using a combination of static and dynamic laser light scattering,we examined the chain diffusion process by following the change of the scattering intensity(i.e.the average molar mass of the particles).For the first time,we have revealed that the diffusion exhibits three stages.In the first stage,the chain diffusion through the shell is even faster than their translational diffusion in a dilute solution.The three stages respectively correspond to the change of the solution in the core from concentrated to semidilute and then from semidilute to dilute. 相似文献
110.
We have developed a method for fabricating microfluidic devices with multi-height structures using single step photolithography. The whole fabrication process is executed by conventional printed circuit board (PCB) technology without the need of having access to clean room facilities. Specifically designed "windows" and "rims" architectures were printed on films that were used as photomasks. Different levels of protruding features on the PCB master were produced by exposing a photomask followed by chemical wet etching. Poly(dimethylsiloxane) (PDMS) was then moulded against the positive relief master to generate microfluidic structures. In this report, we described the fabrication of a microfluidic device featured with a multi-height "sandbag" structure for particle entrapment and peripheral microchannels. Controlled immobilization of biological cells and immunocytochemcial staining assays were performed to demonstrate the applicability of the microfluidic device for cellular analysis. The integrity of the microdevice remained stable under applied pressure, indicating the robustness of the elastic PDMS structures for analytical operation. The simple microfabrication process requires only low-cost materials and minimal specialized equipment and can reproducibly produce mask lines of about 20 microm in width, which is sufficient for most microfluidic applications. 相似文献