全文获取类型
收费全文 | 1128篇 |
免费 | 158篇 |
国内免费 | 59篇 |
专业分类
化学 | 1276篇 |
晶体学 | 1篇 |
力学 | 6篇 |
数学 | 1篇 |
物理学 | 61篇 |
出版年
2024年 | 7篇 |
2023年 | 20篇 |
2022年 | 32篇 |
2021年 | 26篇 |
2020年 | 35篇 |
2019年 | 43篇 |
2018年 | 23篇 |
2017年 | 25篇 |
2016年 | 54篇 |
2015年 | 69篇 |
2014年 | 70篇 |
2013年 | 74篇 |
2012年 | 54篇 |
2011年 | 82篇 |
2010年 | 77篇 |
2009年 | 83篇 |
2008年 | 72篇 |
2007年 | 73篇 |
2006年 | 77篇 |
2005年 | 85篇 |
2004年 | 79篇 |
2003年 | 75篇 |
2002年 | 52篇 |
2001年 | 12篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 12篇 |
1996年 | 8篇 |
1995年 | 6篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
排序方式: 共有1345条查询结果,搜索用时 15 毫秒
31.
Nicola Armaroli Gianluca Accorsi JohnN. Clifford Jean‐Franois Eckert Jean‐Franois Nierengarten 《化学:亚洲杂志》2006,1(4):564-574
Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C60 by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C60G1 – C60G4 , reaching a 99:1 ratio for C60G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C60G1 – C60G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C60 singlet energy transfer. In CH2Cl2, the OPV→C60 electron transfer from the lowest fullerene singlet level (1C60*) is slightly exergonic (ΔGCS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C60G2 – C60G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C60 electron transfer observed for C60G3 and C60G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer. 相似文献
32.
V.L. Furer A.E. Vandyukov J.P. Majoral A.M. Caminade V.I. Kovalenko 《Vibrational Spectroscopy》2006,40(2):155-160
The Raman (10–3500 cm−1) and infrared (150–3500 cm−1) spectra have been recorded for tris(4-oxibenzaldehyde)thiophosphate. This compound includes structural parts of elementoorganic dendrimers: a core and terminal aldehyde groups. The structural optimization and normal mode analysis are performed for elementoorganic dendrimer on the basis of the ab initio density functional theory. It is found that the dendrimer exist in a single stable conformation with planar C6H4CHO fragments. Our calculations show that conformer with one trans and two gauche 4-oxibenzaldehyde groups is realized. All these observations suggest that steric congestion does not disturb the construction of dendrimers even for the highest generations, and that terminal groups are readily available for further reactions. Relying on DFT calculations a complete vibrational assignment is proposed for different parts of the studied dendrimers. 相似文献
33.
Nithyanandhan J Jayaraman N Davis R Das S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):689-698
A series of azobenzene-functionalized poly(alkyl aryl ether) dendrimers have been synthesized and their photochemical and photophysical properties in solution and as thin films have been investigated. Although the photochemical behavior of the azodendrimers in solution indicated that the azobenzene units behave independently, very similar to the constituent monomer azobenzene unit, the properties of thin solid films of the dendrimers were distinctly different. The azodendrimers, AzoG1, AzoG2, and AzoG3 were observed to form stable supercooled glasses, which showed long-wavelength absorption and red emission characteristics of J-aggregates of the azobenzene chromophores. Reversible photoinduced isomerization of the azodendrimers in the glassy state is described. 相似文献
34.
Laurent Griffe Dr. Mary Poupot Dr. Patrice Marchand Dr. Alexandrine Maraval Dr. Cédric‐Olivier Turrin Dr. Olivier Rolland Pascal Métivier Dr. Gérard Bacquet Dr. Jean‐Jacques Fournié Dr. Anne‐Marie Caminade Dr. Rémy Poupot Dr. Jean‐Pierre Majoral Dr. 《Angewandte Chemie (International ed. in English)》2007,46(14):2334-2334
35.
Wang C Zhu G Li J Cai X Wei Y Zhang D Qiu S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):4975-4982
We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere. 相似文献
36.
We report in this study the presence of Janus particles, which are candidates for use with electronic color papers. We used negatively charged polystyrene particles (370 nm) as the core particles, and gold was then sputtered onto their packed monolayer under several conditions. The sputtered particles were next redispersed into the aqueous medium by gentle sonication. Gold nanoparticles localized on one side of the cores could also serve as seeds for subsequent shell growth by electroless gold plating. Through these treatments, a series of well-dispersed Janus particles were obtained with gold nanostructures of different size and shape only on one side. Their dispersions showed different colors originating from the surface plasmon resonance absorption of gold nanoparticles localized on the hemisphere. The particles obtained by this approach have potential applications such as in sensors and electronic color paper. 相似文献
37.
38.
Li Zhao Qiangjun Ling Xiong Liu Chaodong Hang Qiuxia Zhao Fangfei Liu Haibin Gu 《应用有机金属化学》2018,32(2)
Owing to their unique broken symmetry, amphiphilic Janus dendrimers and dendons provide fascinating properties for material, biological, pharmaceutical and biomedical applications. The integration of various organometallic moieties into these macromolecules will further offer the opportunity to form complex and intelligent architectures and materials. Here, we report a novel, simple and multifunctional Janus dendron containing redox‐reversible hydrophobic ferrocene (Fc) unit, complexing‐effective 1,2,3‐triazole ligand and biocompatible hydrophilic triethylene glycol termini. Silver and gold nanoparticles were firstly successfully prepared by using the Janus dendron as the reducing agent of Au(III) and Ag(I), and the stabilizer of the corresponding nanoparticles. The redox response of the Fc moiety was then employed to trigger the release of model drug, rhodamine B, encapsulated in supramolecular micelles formed by the self‐assembly of the Janus dendron. Finally, the precise and excellent metal‐complexing ability of the triazole group in this dendron was fully utilized to stabilize a water‐soluble Cu(I) catalyst, forming supramolecular nanoreactors for the catalysis of the copper(I)‐catalyzed azide alkyne cycloaddition click reaction in only water. The multifunctional characteristics of this dendron highlight the potential for organometallic Janus dendrimers and dendrons in the fields of functional materials and nanomedicines. 相似文献
39.
40.
Julien Iehl Thi Le Anh Nguyen Stéphane Frein Uwe Hahn Joaquín Barberá Jean-François Nierengarten 《Liquid crystals》2017,44(12-13):1852-1860
ABSTRACTLiquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C60) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, 1H and 13C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C60 functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C60 decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C60 is a unique synthetic platform for the design of fullerodendrimers and dendronised materials. 相似文献