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21.
Emission of volatile sesquiterpenes and monoterpenes in grapevine genotypes following Plasmopara viticola inoculation in vitro 下载免费PDF全文
Alberto Algarra Alarcon Valentina Lazazzara Luca Cappellin Pier Luigi Bianchedi Rainer Schuhmacher Georg Wohlfahrt Ilaria Pertot Franco Biasioli Michele Perazzolli 《Journal of mass spectrometry : JMS》2015,50(8):1013-1022
The grapevine (Vitis vinifera) is one of the most widely cultivated fruit crops globally, and one of its most important diseases in terms of economic losses is downy mildew, caused by Plasmopara viticola. Several wild Vitis species have been found to be resistant to this pathogen and have been used in breeding programs to introduce resistance traits to susceptible cultivars. Plant defense is based on different mechanisms, and volatile organic compounds (VOCs) play a major role in the response to insects and pathogens. Although grapevine resistance mechanisms and the production of secondary metabolites have been widely characterized in resistant genotypes, the emission of VOCs has not yet been investigated following P. viticola inoculation. A Proton Transfer Reaction‐Time of Flight‐Mass Spectrometer (PTR‐ToF‐MS) was used to analyze the VOCs emitted by in vitro‐grown plants of grapevine genotypes with different levels of resistance. Downy mildew inoculation significantly increased the emission of monoterpenes and sesquiterpenes by the resistant SO4 and Kober 5BB genotypes, but not by the susceptible V. vinifera Pinot noir. Volatile terpenes were implicated in plant defense responses against pathogens, suggesting that they could play a major role in the resistance against downy mildew by direct toxicity or by inducing grapevine resistance. The grapevine genotypes differed in terms of the VOC emission pattern of both inoculated and uninoculated plants, indicating that PTR‐ToF‐MS could be used to screen hybrids with different levels of downy mildew resistance. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
22.
Sunlight‐Driven Formation and Dissociation of a Dynamic Mixed‐Valence Thallium(III)/Thallium(I) Porphyrin Complex 下载免费PDF全文
Victoria Ndoyom Luca Fusaro Vincent Dorcet Bernard Boitrel Stéphane Le Gac 《Angewandte Chemie (International ed. in English)》2015,54(12):3806-3811
Inspired by a Newton’s cradle device and interested in the development of redox‐controllable bimetallic molecular switches, a mixed‐valence thallium(III)/thallium(I) bis‐strap porphyrin complex, with TlIII bound out of the plane of the N core and TlI hung to a strap on the opposite side, was formed by the addition of TlOAc to the free base and exposure to indirect sunlight. In this process, oxygen photosensitization by the porphyrin allows the oxidation of TlI to TlIII. The bimetallic complex is dynamic as the metals exchange their positions symmetrically to the porphyrin plane with TlIII funneling through the macrocycle. Further exposure of the complex to direct sunlight leads to thallium dissociation and to total recovery of the free base. Hence, the porphyrin plays a key role at all stages of the cycle of the complex: It hosts two metal ions, and by absorbing light, it allows the formation and dissociation of TlIII. These results constitute the basis for the further design of innovative light‐driven bimetallic molecular devices. 相似文献
23.
Catalytic Asymmetric Reactions of 4‐Substituted Indoles with Nitroethene: A Direct Entry to Ergot Alkaloid Structures 下载免费PDF全文
Simone Romanini Emilio Galletti Dr. Lorenzo Caruana Prof. Andrea Mazzanti Prof. Fahmi Himo Dr. Stefano Santoro Prof. Mariafrancesca Fochi Prof. Luca Bernardi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17578-17582
A domino Friedel–Crafts/nitro‐Michael reaction between 4‐substituted indoles and nitroethene is presented. The reaction is catalyzed by BINOL‐derived phosphoric acid catalysts, and delivers the corresponding 3,4‐ring‐fused indoles with very good results in terms of yields and diastereo‐ and enantioselectivities. The tricyclic benzo[cd]indole products bear a nitro group at the right position to serve as precursors of ergot alkaloids, as demonstrated by the formal synthesis of 6,7‐secoagroclavine from one of the adducts. DFT calculations suggest that the outcome of the reaction stems from the preferential evolution of a key nitronic acid intermediate through a nucleophilic addition pathway, rather than to the expected “quenching” through protonation. 相似文献
24.
The Cage Structure of IndanCHF3 is Based on the Cooperative Effects of CH⋅⋅⋅π and CH⋅⋅⋅F Weak Hydrogen Bonds 下载免费PDF全文
Dr. Laura B. Favero Weixing Li Lorenzo Spada Dr. Luca Evangelisti Giorgio Visentin Prof. Dr. Walther Caminati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):15970-15973
The structural and energetic features of the C?H???π interaction and the internal dynamics of the CHF3 group change drastically in going from benzene?CHF3 to indan?CHF3, according to the analysis of the rotational spectrum of the latter complex generated in a supersonic expansion. 相似文献
25.
Organocatalytic,Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene‐Embedding Linear and Angular Polycycles 下载免费PDF全文
Dr. Nicoletta Brindani Dr. Gloria Rassu Dr. Luca Dell'Amico Dr. Vincenzo Zambrano Dr. Luigi Pinna Dr. Claudio Curti Dr. Andrea Sartori Prof. Dr. Lucia Battistini Prof. Dr. Giovanni Casiraghi Prof. Dr. Giorgio Pelosi Dr. Daniela Greco Prof. Dr. Franca Zanardi 《Angewandte Chemie (International ed. in English)》2015,54(25):7386-7390
A direct aminocatalytic synthesis has been developed for the chemo‐, regio‐, diastereo‐, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable π‐extended allylidenemalononitriles as electron‐rich 1,3‐diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic α,β‐unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6‐, 5,6‐, 7,6‐, 6,6,6‐, and 6,5,6‐fused ring systems, as well as biorelevant steroid‐like 6,6,6,6,5‐ and 6,6,6,5,6‐rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bis‐vinylogous Michael/Michael/retro‐Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated. 相似文献
26.
27.
Sol‐to‐Gel Transition in Fast Evaporating Systems Observed by in Situ Time‐Resolved Infrared Spectroscopy 下载免费PDF全文
Prof. Dr. Plinio Innocenzi Dr. Luca Malfatti Dr. Davide Carboni Prof. Dr. Masahide Takahashi 《Chemphyschem》2015,16(9):1933-1939
The in situ observation of a sol‐to‐gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl4 as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time‐resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol‐to‐gel transition. 相似文献
28.
29.
Simone Zanella Dr. Michele Mingozzi Alberto Dal Corso Dr. Roberto Fanelli Dr. Daniela Arosio Prof. Dr. Marco Cosentino Dr. Laura Schembri Dr. Franca Marino Dr. Marta De Zotti Prof. Dr. Fernando Formaggio Dr. Luca Pignataro Prof. Dr. Laura Belvisi Prof. Dr. Umberto Piarulli Prof. Dr. Cesare Gennari 《ChemistryOpen》2015,4(5):633-641
A dual-action ligand targeting both integrin αVβ3 and vascular endothelial growth factor receptors (VEGFRs), was synthesized via conjugation of a cyclic peptidomimetic αVβ3 Arg-Gly-Asp (RGD) ligand with a decapentapeptide. The latter was obtained from a known VEGFR antagonist by acetylation at the Lys13 side chain. Functionalization of the precursor ligands was carried out in solution and in the solid phase, affording two fragments: an alkyne VEGFR ligand and the azide integrin αVβ3 ligand, which were conjugated by click chemistry. Circular dichroism studies confirmed that both the RGD and VEGFR ligand portions of the dual-action compound substantially adopt the biologically active conformation. In vitro binding assays on isolated integrin αVβ3 and VEGFR-1 showed that the dual-action conjugate retains a good level of affinity for both its target receptors, although with one order of magnitude (10/20 times) decrease in potency. The dual-action ligand strongly inhibited the VEGF-induced morphogenesis in Human Umbilical Vein Endothelial Cells (HUVECs). Remarkably, its efficiency in preventing the formation of new blood vessels was similar to that of the original individual ligands, despite the worse affinity towards integrin αVβ3 and VEGFR-1. 相似文献
30.
Christoph M. Hendrich Sebastian Senn Lea Haas Marvin T. Hoffmann Dr. Ute Zschieschang Luca C. Greiner Dr. Frank Rominger Dr. Matthias Rudolph Dr. Hagen Klauk Prof. Dr. Andreas Dreuw Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(59):14778-14784
Herein, we describe a gold-catalyzed cascade cyclization of Boc-protected benzylamines bearing two tethered alkyne moieties in a domino reaction initiated by a 6-endo-dig cyclization. The reaction was screened intensively, and the scope was explored, resulting in nine new Boc-protected dihydrobenzo[c]phenanthridines with yields of up to 98 %; even a π-extension and two bidirectional approaches were successful. Furthermore, thermal cleavage of the Boc group and subsequent oxidation gave substituted benzo[c]phenanthridines in up to quantitative yields. Two bidirectional approaches under the optimized conditions were successful, and the resulting π-extended molecules were tested as organic semiconductors in organic thin-film transistors. 相似文献