全文获取类型
收费全文 | 1386篇 |
免费 | 22篇 |
国内免费 | 130篇 |
专业分类
化学 | 1451篇 |
晶体学 | 21篇 |
力学 | 3篇 |
综合类 | 2篇 |
数学 | 5篇 |
物理学 | 56篇 |
出版年
2024年 | 2篇 |
2023年 | 139篇 |
2022年 | 22篇 |
2021年 | 46篇 |
2020年 | 51篇 |
2019年 | 43篇 |
2018年 | 49篇 |
2017年 | 56篇 |
2016年 | 38篇 |
2015年 | 21篇 |
2014年 | 34篇 |
2013年 | 71篇 |
2012年 | 141篇 |
2011年 | 77篇 |
2010年 | 76篇 |
2009年 | 84篇 |
2008年 | 94篇 |
2007年 | 105篇 |
2006年 | 84篇 |
2005年 | 58篇 |
2004年 | 44篇 |
2003年 | 25篇 |
2002年 | 14篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 51篇 |
1998年 | 51篇 |
1997年 | 3篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 5篇 |
1988年 | 1篇 |
1986年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有1538条查询结果,搜索用时 15 毫秒
41.
《Tetrahedron letters》2019,60(52):151357
In this work, the host–guest interaction between calixpyridinium and the anionic anticancer drug methotrexate disodium was explored in water. Unexpectedly, an interesting anisotropic needle-like rather than an ordinary isotropic spherical supramolecular amphiphilic assembly was fabricated by the complexation of calixpyridinium with methotrexate disodium. It is the second anionic guest to be discovered to form the non-spherical supramolecular assembly upon complexation with calixpyridinium. This discovery implies the possibility to construct various topological nanostructures based on the host–guest interactions between calixpyridinium and the anionic drugs in the future. The resulting calixpyridinium–drug assemblies with different morphologies may have the diverse potentials to adjust the efficacies of anionic drugs. 相似文献
42.
A photoredox catalytic ensemble consisting of CuO‐Fe2O3 nanocomposites and oligomeric derivative of phenazine has been developed. The prepared system acts as an efficient photoredox catalyst for C?N bond formation reaction via SET mechanism under ‘green’ conditions (aerial environment, mixed aqueous media, recyclable), requiring less equivalents of base and amine substrate. The present study demonstrates the significant role of supramolecular assemblies as photooxidants and reductants upon irradiation and their important contribution towards the activation of the metallic centre through energy transfer and electron transfer pathways. The potential of oligomer 4 : CuO‐Fe2O3 has also been explored for C?C bond formation reactions via the Sonogashira protocol. 相似文献
43.
Herein, two unit of β-cyclodextrin linked by thiomethylene bridge was synthesized and employed as a novel efficient supramolecular host for the synthesis of biologically active chromenones templates via three-component single-pot reaction. A possible reaction mechanism through molecular complexation is suggested based on 2D ROESY NMR spectroscopic analysis. Moreover, the catalyst could be easily recycled, while a 94% yield and 89% rate of catalyst recovery could be achieved after four cycles of catalyst recycling. Environmentally benign reaction conditions, excellent yields, and avoidance of organic solvent and conventional isolation as well as purification are the noteworthy credits of this developed protocol. 相似文献
44.
Bosco Christin Maria Arputham Ashwin Chokalingam Saravanan Marimuthu Senthilkumaran Ragupathi Sumathi Palanisamy Suresh 《Supramolecular chemistry》2018,30(1):32-41
The host–guest interaction of α-tocopherol (vitamin E) with p-sulfonatocalix[4]arene (p-SC4) in solution state is studied using emission and cyclic voltammetric techniques. The lipid soluble α-tocopherol (α-T) forms a solid complex with p-SC4. FTIR and NMR spectral analysis of the solid complex reveals the tight packing of α-T inside the cavity of p-SC4. The structural deformation is confirmed by XRD analysis. SEM images differentiate the highly porous gel like structure of vitamin E aggregate and the solid structure of the host–guest complex prepared. NOESY spectra confirm the tight penetration of α-T within the hydrophobic cavity of p-SC4. 相似文献
45.
A hybrid system containing a pillar[5]arene unit and ten crown ether moieties was developed. The LCST behavior and thermo-responsiveness were successfully introduced into this pillar[5]arene-crown ether system. Both host-guest interactions and salting-out effect displayed great effects in realizing the supramolecular control over LCST properties and thermo-responsiveness. Compared with the individual macrocycles, this hybrid macrocycle system dramatically amplified the supramolecular control effect over LCST behavior. 相似文献
46.
A 3D supramolecular complex [Co(III)(Phen)2Cl2][DNQ]Cl·H2O (DNQ = 6,7-dinitroquinoxaline-2,3-dione) has been synthesized and determined by single-crystal X-ray analysis. Anion binding studies carried out using 1H NMR and UV-visible revealed that a genuine hydrogen bond interaction between anion receptor 2 and Cl? can be detected, but fluoride is deprotonating the anion receptor 2. X-ray analysis results show that it is not possible for the two amide nitrogen atoms of anion receptor to form hydrogen bonds to a chloride ion in the presence of small aliquots of water. 相似文献
47.
Arno M. Bieser 《Supramolecular chemistry》2013,25(4):363-367
This article highlights the aggregation behaviour of potential low molecular weight hydrogelators on attracting surfaces. Our goal was the development of a method, which enables the finding of new hydrogelators that are not easily recognizable as such because they only form instable or no hydrogels in aqueous solution. To this end, a series of negatively charges azo-dyes was synthesized and positive charged glass slides were immersed into their aqueous solutions. All dyes showed supramolecular organization and significant concentration on the attracting glass surface. Microscopic investigations mostly revealed the formation of crystals. However, one compound, (1-(2-n-octylphenylazo)-2-hydroxy-6-naphthalenesulphonate, selectively formed a hydrogel on the surface whereas it does not gel in aqueous solution. This reveals the hydrogel as the stable form of this compound under equilibrium conditions. This method of surface-induced hydrogelation might facilitate the identification of new hydrogelators. Further more, it might also allow the mimicking of surface gelation as a process of biological relevance. 相似文献
48.
Rosemary Sheehan 《Supramolecular chemistry》2013,25(5):443-451
Computational protocols capable of modelling supramolecular complexes have been evaluated. The complexation of cations by crown ethers and quaternary ammonium ions by an oxacalix[3]arene are presented as examples. In the latter case reliable qualitative results were obtained using the semi-empirical PM3 method where guest LUMO and electrostatic potential energies have been shown to correlate with experimental binding data. The optimal method for more accurate results combines semi-empirical equilibrium geometry and property calculations with single point energy calculations at the HF/6–31G* or BP/6–31G* quantum mechanical level. 相似文献
49.
The complexation of various ammonium ions with a resorcarene host was evaluated by ab initio calculations. The approximations of the binding locations and the interaction energies for each guest are reported. The supramolecular complex formation also affects the conformation of the resorcarene host. 相似文献
50.
The ability of β-cyclodextrin (β-CD), γ-CD, hydroxypropyl-β-CD (HP-β-CD), trimethyl-β-CD (TM-β-CD), sulfurbutylether-β-CD (SBE-β-CD) and carboxymethyl-β-cyclodextrin (CM-β-CD) to break the aggregate of the meso-tetrakis(4-N-trimethylaminobenzyl)porphyrin (TAPP) and to form 2:1 inclusion complexes has been studied by absorption and fluorescence spectroscopy. The formation constants are calculated, respectively, by fluorimetry, from which the inclusion capacity of different CDs is compared and the inclusion mechanism of charged-β-CD (SBE-β-CD and CM-β-CD) is quite different from that of the parent β-CD. At lower pH, the complexation between TM-β-CD and H2TAPP2+ (the form of the diprotonated TAPP) hampers the continuous protonation of the pyrrole nitrogen of TAPP and the hydrophobic cavity may prefer to bind an apolar neutral porphyrin molecule. 1HNMR data support the inclusion conformation of the porphyrin–cyclodextrin supramolecular system, indicating the interaction of the meso-phenyl groups of TAPP with the cavity of CDs. For this host–guest inclusion model, cyclodextrin being regarded as the protein component, which acts as a carrier enveloping the active site of heme prosthetic group within its hydrophobic environment, provides a protective sheath for the porphyrin, creating artificial analogues of heme-containing proteins. However, for TAPP, encapsulated within this saccharide-coated barrier, its photophysical and photochemical properties changed strongly. 相似文献