全文获取类型
收费全文 | 2913篇 |
免费 | 552篇 |
国内免费 | 291篇 |
专业分类
化学 | 2279篇 |
晶体学 | 38篇 |
力学 | 164篇 |
综合类 | 13篇 |
数学 | 255篇 |
物理学 | 1007篇 |
出版年
2024年 | 13篇 |
2023年 | 62篇 |
2022年 | 118篇 |
2021年 | 118篇 |
2020年 | 155篇 |
2019年 | 153篇 |
2018年 | 139篇 |
2017年 | 117篇 |
2016年 | 172篇 |
2015年 | 186篇 |
2014年 | 179篇 |
2013年 | 266篇 |
2012年 | 276篇 |
2011年 | 282篇 |
2010年 | 177篇 |
2009年 | 148篇 |
2008年 | 214篇 |
2007年 | 152篇 |
2006年 | 145篇 |
2005年 | 103篇 |
2004年 | 88篇 |
2003年 | 79篇 |
2002年 | 60篇 |
2001年 | 47篇 |
2000年 | 41篇 |
1999年 | 45篇 |
1998年 | 27篇 |
1997年 | 21篇 |
1996年 | 28篇 |
1995年 | 22篇 |
1994年 | 25篇 |
1993年 | 15篇 |
1992年 | 14篇 |
1991年 | 9篇 |
1990年 | 20篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1980年 | 1篇 |
排序方式: 共有3756条查询结果,搜索用时 0 毫秒
51.
Lu C Wei F Wu N Huang L Zhao X Jiao X Luo C Cao W 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):974-977
A kind of hybrid multilayer film based on mercaptobenzoic acid-capped Au nanoparticles (MBA-Au-NPs) and photoreactive nitrodiazoresin (NDR) has been fabricated via electrostatic self-assembly. Upon exposure to UV light, the initial ionic bonds between the layers of the film convert into covalent bonds and the film stability toward polar solvents, salt, or surfactant solutions increases significantly. The micropatterned NDR/MBA-Au-NP film with the covalently linked architecture was formed by selecting exposure of the film through a photomask and later developed in sodium dodecyl sulfate (SDS) aqueous solution. The metallic Au-NP micropatterns, furthermore, are produced by sintering the micropatterned NDR/MBA-Au-NP film at 550 degrees C, at which the organic components are removed completely. The well-defined micropatterns were characterized with atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), microscope with a charge-coupled device (CCD) camera, and X-ray photoelectron spectroscopy (XPS). 相似文献
52.
Solution self-assembly, spontaneous deprotonation, and crystal structures of bipyrazolate-bridged metallomacrocycles with dimetal centers 总被引:5,自引:0,他引:5
Yu SY Huang HP Li SH Jiao Q Li YZ Wu B Sei Y Yamaguchi K Pan YJ Ma HW 《Inorganic chemistry》2005,44(25):9471-9488
A series of nanosized cavity-containing bipyrazolate-bridged metallomacrocycles with dimetal centers, namely, {[(bpy)M]8L4}(NO3)8 [L=3,3',5,5'-tetramethyl-4,4'-bipyrazolyl, Pd, Pt; 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene), Pd; and 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbiphenyl, Pd], {[(phen)M]8L4}(NO3)8 [L=3,3',5,5'-tetramethyl-4,4'-bipyrazolyl, Pd, Pt; 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, Pd; and 1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbiphenyl, Pd], {[(bpy)Pd]6L3}(NO3)6 [L=1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,], {[(phen)Pd]6L3}(NO3)6 [L=1,4-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,], {[(bpy)Pd]4L2}(NO3)4 [L=1,3-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, and 1,2-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,], and {[(phen)Pd]4L2}(NO3)4 [L=1,3-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene, and 1,2-bis-4'-(3',5'-dimethyl)-pyrazolylbenzene,] (where bpy=2,2'-bipyridine and phen=1,10-phenanthroline) have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1H-bipyrazolyl ligands in aqueous solution. These complexes, with weak Pd(II)...Pd(II) or Pt(II)...Pt(II) interactions, have been characterized by elemental analysis, 1H and 13C NMR, cold-spray ionization or electrospray ionization mass spectrometry, UV-visible spectroscopy, and luminescence spectroscopy. Complexes and have also been characterized by single-crystal X-ray diffraction analysis. 相似文献
53.
54.
Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N3) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd2(L1)2(N3)2(μ‐1,1‐N3)2] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd2(L2)2(N3)2(μ‐1,1‐N3)2] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd2(L3)2(NCS)2(μ1,3‐NCS)2] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures. 相似文献
55.
The generation of vinyl or aryl radicals under classical, thermal AIBN/n-Bu(3)SnH conditions at 80 degrees C in the presence of an excess of (MeO)(3)P gives rise to the corresponding vinyl- or arylphosphonates in good yields. This approach complements the photochemical reactions of the same systems previously used. Reactions with the individual stereoisomers of MeCH=CHMeBr (thermal AIBN/n-Bu(3)SnH conditions) afford a radical-equilibrated 96/4 E/Z ratio of vinylphosphonates. Substitution of (TMS)(3)SiH for n-Bu(3)SnH yields an approximately 1/1 ratio of separable E and Z vinylphosphonate diastereomers. 相似文献
56.
Three hexakis(imidazole)metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co(Im)6]C12·2HCl·2H2O (1) and [Ni(Im)6]C12·4H2O (3) [Im=imidazole] could interact with DNA mainly by intercalation. 相似文献
57.
微波辐射下LaNaY沸石的水热交换反应 总被引:8,自引:0,他引:8
报道微波辐射应用于NaY沸石与La(NO_3)_3溶液的离子交换反应,结果表明微波辐射可提高La ̄+的交换度,缩短交换时间。 相似文献
58.
Density functional theory calculations have been carried out on the CO/H2 coadsorption on the (001), (110), and (100) surfaces of Fe5C2 for the understanding of the Fischer-Tropsch synthesis (FTS) mechanism. The stable surface species changes with the variation of the H2 and CO coverage. Along with dissociated hydrogen and adsorbed CO in 2-, 3-, and 4-fold configurations, methylidyne (C(s)H) (C(s), surface carbon), ketenylidene (C(s)CO), ketenyl (C(s)HCO), ketene (C(s)H2CO), and carbon suboxide (C(s)C2O2) are computed as thermodynamically stable surface species on Fe5C2(001) and Fe5C2(110) containing both surface iron and carbon atoms. These surface carbon species can be considered as the preliminary stages for FTS. On Fe5C2(100) with only iron atoms on the surface layer, the stable surface species is dissociated hydrogen and CO with top and 2-fold configurations. The bonding nature of these adsorbed carbon species has been analyzed. 相似文献
59.
Dan Su Dingsheng Yu Liping Hu Shuke Jiao 《Journal of polymer science. Part A, Polymer chemistry》1989,27(11):3769-3778
The effects of five ethers and four AliBu2OR's with varied R' on butadiene–propylene alternating copolymerization were investigated. It was found that by adding the proper third component, both the conversion and the catalytic efficiency could be increased. The effect of the third component on the valence state of vanadium ion was also studied. A model of the active center of the ternary-component catalyst system was proposed. 相似文献
60.
Tiantian Liu Xiaojie Chen Juan Zhao Weichun Wei Zhu Mao William Wu Shibo Jiao Yang Liu Zhiyong Yang Zhenguo Chi 《Chemical science》2021,12(14):5171
Pure organic emitters with full utilization of triplet excitons are in high demand for organic light-emitting diodes (OLEDs). Herein, through modulation of electron donors and introduction of phenyl rings as π spacers, we present three pure organic fluorophores (BCz, BTCz and BPTCz) with the hybridized local and charge-transfer (HLCT) excited state feature for OLED fabrication. Importantly, the introduction of π spacers in BPTCz not only enhances locally excited character with a fast radiative decay but also promotes intermolecular interactions to suppress non-radiative decays, contributing to a high solid-state fluorescence efficiency over 90%. Significantly, BPTCz not only endows its doped OLEDs with an external quantum efficiency (EQE) up to 19.5%, but also its non-doped OLED with a high EQE of 17.8%, and these outstanding efficiencies are the state-of-the-art performances of HLCT-based OLEDs.Three purely organic fluorophores with a hybridized local and charge-transfer excited state feature are presented and enabled organic light-emitting diodes with record high external quantum efficiencies close to 20%. 相似文献