全文获取类型
收费全文 | 1540篇 |
免费 | 43篇 |
国内免费 | 163篇 |
专业分类
化学 | 1647篇 |
晶体学 | 23篇 |
力学 | 2篇 |
综合类 | 1篇 |
数学 | 3篇 |
物理学 | 70篇 |
出版年
2024年 | 2篇 |
2023年 | 138篇 |
2022年 | 24篇 |
2021年 | 46篇 |
2020年 | 68篇 |
2019年 | 46篇 |
2018年 | 53篇 |
2017年 | 61篇 |
2016年 | 45篇 |
2015年 | 29篇 |
2014年 | 44篇 |
2013年 | 92篇 |
2012年 | 152篇 |
2011年 | 91篇 |
2010年 | 84篇 |
2009年 | 95篇 |
2008年 | 105篇 |
2007年 | 120篇 |
2006年 | 95篇 |
2005年 | 73篇 |
2004年 | 56篇 |
2003年 | 37篇 |
2002年 | 19篇 |
2001年 | 20篇 |
2000年 | 16篇 |
1999年 | 51篇 |
1998年 | 51篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1990年 | 5篇 |
1988年 | 1篇 |
1986年 | 2篇 |
排序方式: 共有1746条查询结果,搜索用时 109 毫秒
131.
《中国化学会会志》2017,64(4):404-411
The bridged tetracopper(I) complex [{Cu2(μ‐dppm)2}2(μ‐(1,3‐O2CC6H4 (CO2 )2)](BF4 )2 ( 2 (BF4 )2) was prepared. This complex and the neutral dipyridyl compounds (NN ; NN = 4,4′‐bipyridine (bpy), 1,2‐bis(4‐pyridyl)ethane (bpa), 4,4′‐trimethylenedipyridine (tmp)) can form dynamic equilibria in CH2Cl2 . From the equilibrium mixtures containing 2 (BF4 )2 and NN with 2 (BF4 )2/NN = 1:1, different supramolecular compounds were obtained as single crystals, and their structure were determined by X‐ray crystallography. The flexibility of NN is found to be important in determining the outcome of the reactions with a rigid bpy, leading to the formation of the coordination polymer [{Cu2(μ‐dppm)2}2(μ‐1,3‐C6H4 (CO2 )2)(μ‐bpy)] n (BF4 )2n ( 3 (BF4 )2n ), whereas with flexible bpa and tmp direct the formation of the metalacages [{Cu2(μ‐dppm)2}2(μ‐1,3‐C6H4 (CO2 )2)(μ‐NN )](BF4 )2 (NN = bpa, 4 (BF4 )2; tmp, 5 (BF4 )2), respectively, as supported by density functional theory (DFT ) calculation results. 相似文献
132.
The first cationic water-soluble pillar[7]arene CWP7 was prepared. 1H NMR, 13C NMR, and MALDI-TOF-MS were performed to provide converging evidences of the structure of obtained CWP7. Host–guest complexation between this novel pillar[7]arene-based host and sodium pyren-1-olate guest G was fully investigated in aqueous solution. Increased fluorescence intensity was observed during the inclusion complexation. Driven by the cooperativity of electrostatic interactions, π-stacking interactions and hydrophilic/hydrophobic interactions, the guest penetrated into the cavity of CWP7 to form a pseudorotaxane-type inclusion complex with relatively high binding affinity. 相似文献
133.
含丁三醇端基富电子醚链与阳离子环蕃超分子准轮烷的表征和性能研究 总被引:1,自引:0,他引:1
以4-(2-(4-(苄氧基)苯氧基)乙氧基)-1,2,3-丁三醇(C)为富电子供体的醚链,与缺电子联吡啶大环化合物环双(百草枯-亚苯基)四阳离子环蕃(CPQT)和四氟取代环蕃(4FCPQT)自组装形成超分子准轮烷C(CPQT)和C(4FCPQT),并利用1HNMR的化学位移变化来研究两种不同准轮烷在温度变化时它们的相互作用。实验结果表明,由于富电子供体的一端含有3个羟基,易和缺电子联吡啶大环形成氢键,因此醚链的丁三醇端不能进入大环;缺电子联吡啶大环的一个苯环上的氢被氟取代后,由于电场力的作用,使富电子供体进入大环的概率相对降低,并使富电子醚链供体穿入大环的位置发生"偏心"作用。 相似文献
134.
Jannis W. Ochsmann Sebastian Lenz Sebastian G. J. Emmerling Ralf S. Kappes Sebastian K. Nett Maria C. Lechmann Stephan V. Roth Jochen S. Gutmann 《Journal of polymer science. Part A, Polymer chemistry》2010,48(14):1569-1573
Thin films of PS-b-PEO block copolymers were utilized as structured reservoirs for localized nanoscale precipitation reactions. By consecutively immersing the film into solutions of thioacetamide and cadmium chloride, we were able to obtain a monolayer of cadmium sulfide nanostructures on top of the block copolymer film. AFM and grazing incidence small angle X-ray scattering revealed spherical nanostructures (d = 15 nm) corresponding to the dimensions given by the block copolymer film. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1569–1573, 2010 相似文献
135.
Di Gao 《Tetrahedron》2010,66(16):2961-12163
Four novel amphiphilic cholesterol-based and sugar-contained low-molecular-mass gelators (LMMGs) were designed and prepared. According to the structures of the linkers, which are ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,6-hexane- diamine, these compounds are denoted as 1, 2, 3 and 4, respectively. Gelation tests revealed that 2, 3 and 4 start to gel xylene at concentrations of 0.090%, 0.022%, and 0.016% (w/v), respectively, which are typical ‘super-gelators’. Moreover, these xylene gel systems also possess film formation property. Scanning electron microscopy (SEM) measurements demonstrated that the aggregation behaviors of the compounds are greatly affected by the structures of the linkers. 1H NMR spectroscopy studies revealed that intermolecular hydrogen bonding formation plays an important role for the formation of the gels. X-ray diffraction (XRD) studies showed that 1 possesses a layered structure in its 1-pentanol gel, a similar structure to that of it in solid state. Gelator 3 also possesses a similar structure in its THF gel, but different from that of it in solid state. Transmission electron microscopy (TEM) observation revealed the helical nature of the nanobelt assemblies of 1 in its 1-pentanol gel. 相似文献
136.
Reaction of 6-chloro-N,N′-bispyrazolyl-[1,3,5]triazine-2,4-diamines with 4-aminobenzylamine under microwave irradiation produces bistriazines in excellent yields. The use of a diamine bearing amino groups with different reactivities allowed the reaction to be carried out in two steps and selectively gave monotriazines, bistriazines with identical substituents and differently substituted bistriazines. The structures of these new compounds have been studied by NMR spectroscopy, mass spectrometry and in one case by X-ray crystallogrphy. These new bistriazines have promising applications in supramolecular chemistry based on hydrogen bonds and/or complexation with metals. The presence of a rigid linker can be used for the efficient preparation of extended supramolecular polymers with interesting fluorescence properties by complexation with cyanuric and barbituric acid derivatives. 相似文献
137.
Flavio S. Damos Rita C.S. Luz Auro A. Tanaka Lauro T. Kubota 《Analytica chimica acta》2010,664(2):144-10063
The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using the host-guest binding of a supramolecular complex at a host surface by combining a self-assembled monolayer (SAM) of mono-(6-deoxy-6-mercapto)-β-cyclodextrin (βCDSH), iron (III) tetra-(N-methyl-4-pyridyl)-porphyrin (FeTMPyP) and cyclodextrin-functionalized gold nanoparticles (CDAuNP). The supramolecular modified electrode showed excellent catalytic activity for oxygen reduction. The reduction potential of oxygen was shifted about 200 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare gold electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves probably 4-electrons with a rate constant (kobs) of 7 × 104 mol−1 L s−1. A linear response range from 0.2 up to 6.5 mg L−1, with a sensitivity of 5.5 μA L mg−1 (or 77.5 μA cm−2 L mg−1) and a detection limit of 0.02 mg L−1 was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 3.0% for 10 measurements of a solution of 6.5 mg L−1 oxygen. 相似文献
138.
An oxacalix[2]arene[2]pyrimidine-bis(ZnII-porphyrin) conjugate was readily prepared via nucleophilic aromatic substitution of a phenolic AB3-Zn-porphyrin on the upper rim of a (1,3-alternate) 5,17-bis(methylsulfonyl)oxacalix[4]arene precursor. Efficient 1:1 complex formation between the ‘jaws’ bisporphyrin tweezer and fullerene C70 was evidenced by 1H NMR titrations (K = 3.0 × 104 M−1), while no detectable complexation could be observed with C60. On the other hand, an analogous oxacalix[4]arene-bis(Cu-corrole) conjugate did not show any measurable (C60 or C70) fullerene binding. 相似文献
139.
Ulf H. Strasser Beate Neumann Hans‐Georg Stammler Norbert W. Mitzel Prof. Dr. 《无机化学与普通化学杂志》2010,636(7):1249-1254
The tetrasilyl ethers calix[4]areneOSiMe2R (R = Me, H, vinyl, allyl) were prepared by salt elimination; the calix[4]arene was deprotonated with sodium hydride and subsequently reacted with chlorosilanes ClSiMe2R. In general, DMF was chosen as solvent in order to steer the reactions in terms of a preference for the cone‐conformation of the products. In the case of calix[4]areneOSiMe3 both, partial‐cone‐ and cone‐conformers, were synthesised. All products were characterised by NMR (1H, 13C, 29Si) spectroscopy, mass spectrometry and single‐crystal X‐ray diffraction. 相似文献
140.
Yan Wang Li-Na Xiao Hong Ding Zhong-Min Gao Tie-Gang Wang Xiao-Bing Cui Ji-Qing Xu 《Journal of solid state chemistry》2010,183(12):2862-2868
Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [WVI3VV3O19H]{[Cu(HDABCO)]2(H2O)} (1), [P2MoVI18O62][HDABCO]2[H2DABCO]2·12 H2O (2) and [MoVI7.5WVI0.5O27][Cu(HDABCO)]2·2 H3O·2 H2O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the “chains” arranged hexagonally, compound 3 contains [Mo7.5W0.5O27]∞ chain decorated by [Cu(HDABCO)]2+ cations, which was then packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks. 相似文献