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61.
Jiaze Xie Jan-Niklas Boyn Alexander S. Filatov Andrew J. McNeece David A. Mazziotti John S. Anderson 《Chemical science》2020,11(4):1066
Here we report that capping the molecule TTFtt (TTFtt = tetrathiafulvalene-2,3,6,7-tetrathiolate) with dialkyl tin groups enables the isolation of a stable series of redox congeners and facile transmetalation to Ni and Pd. TTFtt has been proposed as an attractive building block for molecular materials for two decades as it combines the redox chemistry of TTF and dithiolene units. TTFttH4, however, is inherently unstable and the incorporation of TTFtt units into complexes or materials typically proceeds through the in situ generation of the tetraanion TTFtt4−. Capping of TTFtt4− with Bu2Sn2+ units dramatically improves the stability of the TTFtt moiety and furthermore enables the isolation of a redox series where the TTF core carries the formal charges of 0, +1, and +2. All of these redox congeners show efficient and clean transmetalation to Ni and Pd resulting in an analogous series of bimetallic complexes capped by 1,2-bis(diphenylphosphino)ethane (dppe) ligands. Furthermore, by using the same transmetalation method, we synthesized analogous palladium complexes capped by 1,1′-bis(diphenylphosphino)ferrocene (dppf) which had been previously reported. All of these species have been thoroughly characterized through a systematic survey of chemical and electronic properties by techniques including cyclic voltammetry (CV), ultraviolet-visible-near infrared spectroscopy (UV-vis-NIR), electron paramagnetic resonance spectroscopy (EPR), nuclear magnetic resonance spectroscopy (NMR) and X-ray diffraction (XRD). These detailed synthetic and spectroscopic studies highlight important differences between the transmetalation strategy presented here and previously reported synthetic methods for the installation of TTFtt. In addition, the utility of this stabilization strategy can be illustrated by the observation of unusual TTF radical–radical packing in the solid state and dimerization in the solution state. Theoretical calculations based on variational 2-electron reduced density matrix methods have been used to investigate these unusual interactions and illustrate fundamentally different levels of covalency and overlap depending on the orientations of the TTF cores. Taken together, this work demonstrates that tin-capped TTFtt units are ideal reagents for the installation of redox-tunable TTFtt ligands enabling the generation of entirely new geometric and electronic structures.Capping TTFtt enables facile transmetalation in three different oxidation states. 相似文献
62.
Jeremy M. Kaminski Angela Rodríguez-Serrano Fabian Dinkelbach Hector Miranda-Salinas Andrew P. Monkman Christel M. Marian 《Chemical science》2022,13(23):7057
Quantum chemical studies employing combined density functional and multireference configuration interaction methods suggest five excited electronic states to be involved in the prompt and delayed fluorescence emission of TpAT-tFFO. Three of them, a pair of singlet and triplet charge transfer (CT) states (S1 and T1) and a locally excited (LE) triplet state (T3), can be associated with the (Me → N) conformer, the other two CT-type states (S2 and T2) form the lowest excited singlet and triplet states of the (Me → Ph) conformer. The two conformers, which differ in essence by the shearing angle of the face-to-face aligned donor and acceptor moieties, are easily interconverted in the electronic ground state whereas the reorganization energy is substantial in the excited singlet state, thus explaining the two experimentally observed time constants of prompt fluorescence emission. Forward and reverse intersystem crossing between the singlet and triplet CT states is mediated by vibronic spin–orbit interactions involving the LE T3 state. Low-frequency vibrational modes altering the distance and alignment of the donor and acceptor π-systems tune the S1 and T3 states (likewise S2 and T3) into and out of resonance. The enhancement of intersystem crossing due to the interplay of vibronic and spin–orbit coupling is considered a general feature of organic through-space charge-transfer thermally activated delayed fluorescence emitters.DFT/MRCI quantum chemical studies suggest five excited electronic states to be involved in the prompt and delayed fluorescence emission of TpAT-tFFO. 相似文献
63.
Yang Sung Sohn Anat losub-Amir Alfredo E. Cardenas Ola Karmi Merav Darash Yahana Tal Gruman Linda Rowland Henri-Baptiste Marjault Lauren J. Webb Ron Mittler Ron Elber Assaf Friedler Rachel Nechushtai 《Chemical science》2022,13(23):6929
An effective anti-cancer therapy should exclusively target cancer cells and trigger in them a broad spectrum of cell death pathways that will prevent avoidance. Here, we present a new approach in cancer therapy that specifically targets the mitochondria and ER of cancer cells. We developed a peptide derived from the flexible and transmembrane domains of the human protein NAF-1/CISD2. This peptide (NAF-144-67) specifically permeates through the plasma membranes of human epithelial breast cancer cells, abolishes their mitochondria and ER, and triggers cell death with characteristics of apoptosis, ferroptosis and necroptosis. In vivo analysis revealed that the peptide significantly decreases tumor growth in mice carrying xenograft human tumors. Computational simulations of cancer vs. normal cell membranes reveal that the specificity of the peptide to cancer cells is due to its selective recognition of their membrane composition. NAF-144-67 represents a promising anti-cancer lead compound that acts via a unique mechanism.An effective anti-cancer therapy should exclusively target cancer cells and trigger in them a broad spectrum of cell death pathways that will prevent avoidance. 相似文献
64.
Shengying Lin Xiaoyang Wang Roy Wai-Lun Tang Hung Chun Lee Ho Hin Chan Sheyne S. A. Choi Tina Ting-Xia Dong Ka Wing Leung Sarah E. Webb Andrew L. Miller Karl Wah-Keung Tsim 《Molecules (Basel, Switzerland)》2022,27(12)
COVID-19, resulting from infection by the SARS-CoV-2 virus, caused a contagious pandemic. Even with the current vaccines, there is still an urgent need to develop effective pharmacological treatments against this deadly disease. Here, we show that the water and ethanol extracts of the root and rhizome of Polygonum cuspidatum (Polygoni Cuspidati Rhizoma et Radix), a common Chinese herbal medicine, blocked the entry of wild-type and the omicron variant of the SARS-CoV-2 pseudotyped virus into fibroblasts or zebrafish larvae, with IC50 values ranging from 0.015 to 0.04 mg/mL. The extracts were shown to inhibit various aspects of the pseudovirus entry, including the interaction between the spike protein (S-protein) and the angiotensin-converting enzyme II (ACE2) receptor, and the 3CL protease activity. Out of the chemical compounds tested in this report, gallic acid, a phytochemical in P. cuspidatum, was shown to have a significant anti-viral effect. Therefore, this might be responsible, at least in part, for the anti-viral efficacy of the herbal extract. Together, our data suggest that the extracts of P. cuspidatum inhibit the entry of wild-type and the omicron variant of SARS-CoV-2, and so they could be considered as potent treatments against COVID-19. 相似文献
65.
Christopher J. H. Smalley Harriet E. Hoskyns Colan E. Hughes Duncan N. Johnstone Tom Willhammar Mark T. Young Christopher J. Pickard Andrew J. Logsdail Paul A. Midgley Kenneth D. M. Harris 《Chemical science》2022,13(18):5277
We report the crystal structure of a new polymorph of l-tyrosine (denoted the β polymorph), prepared by crystallization from the gas phase following vacuum sublimation. Structure determination was carried out by combined analysis of three-dimensional electron diffraction (3D-ED) data and powder X-ray diffraction (XRD) data. Specifically, 3D-ED data were required for reliable unit cell determination and space group assignment, with structure solution carried out independently from both 3D-ED data and powder XRD data, using the direct-space strategy for structure solution implemented using a genetic algorithm. Structure refinement was carried out both from powder XRD data, using the Rietveld profile refinement technique, and from 3D-ED data. The final refined structure was validated both by periodic DFT-D calculations, which confirm that the structure corresponds to an energy minimum on the energy landscape, and by the fact that the values of isotropic 13C NMR chemical shifts calculated for the crystal structure using DFT-D methodology are in good agreement with the experimental high-resolution solid-state 13C NMR spectrum. Based on DFT-D calculations using the PBE0-MBD method, the β polymorph is meta-stable with respect to the previously reported crystal structure of l-tyrosine (now denoted the α polymorph). Crystal structure prediction calculations using the AIRSS approach suggest that there are three other plausible crystalline polymorphs of l-tyrosine, with higher energy than the α and β polymorphs.A new polymorph of l-tyrosine is reported, with the crystal structure determined by combined analysis of 3D-ED data and powder XRD data, augmented by information from periodic DFT-D calculations and solid-state 13C NMR data. 相似文献
66.
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68.
Yevgeniy Frenkel Andrew J. Majda Boualem Khouider 《Theoretical and Computational Fluid Dynamics》2013,27(3-4):533-559
This paper presents a study of the diurnal cycle of tropical precipitation and its interaction with convectively coupled waves in the context of simple models with crude vertical resolution. One and two baroclinic mode models are tested in both the context of a one-column model and the context of a full spatial dependency that permits waves to propagate and interact with the diurnal cycle. It is found that a one baroclinic mode model is capable of reproducing a realistic diurnal cycle of tropical precipitation both over land and over the ocean provided an adequate switch function is used to mimic the congestus preconditioning mechanism that operates in the multicloud model of Khouider and Majda. However, a full two baroclinic mode multicloud model is needed to capture the interaction of convectively coupled tropical waves with the diurnal cycle. In a more conventional mass flux parameterization framework, both one and two baroclinic mode models fail to capture the diurnal cycle of tropical precipitation. 相似文献
69.
Andrew P. Jackson Brian J. Alloway 《International journal of environmental analytical chemistry》2013,93(3-4):119-131
Abstract Pressure decomposition in a microwave oven provides a rapid means of sample preparation for plant tissue analyses. The use of delayed atomisation cuvettes, Smith-Hieftje background correction and matrix/analyte modification enables accurate determinations of cadmium concentrations in plant materials to be made. However, care should be taken to restrict the concentrations of modifier used, as too high a concentration may lead to problems with both tube life and over-correction by the Smith-Hieftje background correction system. 相似文献
70.
Sylvain Laclef Katie Anderson Andrew J.P. White Anthony G.M. Barrett 《Tetrahedron letters》2012,53(2):225-227
The total synthesis of amorfrutin A, a prenyl bibenzyl natural product has been achieved in five steps from 2,2,6-trimethyl-4H-1,3-dioxin-4-one. The key step of the synthesis is an efficient palladium(0)-catalyzed decarboxylative prenylation migration and aromatization sequence. 相似文献