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991.
Timothy R. Wilson Malavikha Rajivmoorthy Jordan Goss Sam Riddle Prof. Mark E. Eberhart 《Chemphyschem》2019,20(24):3289-3305
Our curiosity-driven desire to “see” chemical bonds dates back at least one-hundred years, perhaps to antiquity. Sweeping improvements in the accuracy of measured and predicted electron charge densities, alongside our largely bondcentric understanding of molecules and materials, heighten this desire with means and significance. Here we present a method for analyzing chemical bonds and their energy distributions in a two-dimensional projected space called the condensed charge density. Bond “silhouettes” in the condensed charge density can be reverse-projected to reveal precise three-dimensional bonding regions we call bond bundles. We show that delocalized metallic bonds and organic covalent bonds alike can be objectively analyzed, the formation of bonds observed, and that the crystallographic structure of simple metals can be rationalized in terms of bond bundle structure. Our method also reproduces the expected results of organic chemistry, enabling the recontextualization of existing bond models from a charge density perspective. 相似文献
992.
Joseph P. Tassone Emma V. England Preston M. MacQueen Michael J. Ferguson Mark Stradiotto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(8):2507-2511
The base metal‐catalyzed C?N cross‐coupling of bulky α,α,α‐trisubstituted primary alkylamines with (hetero)aryl electrophiles represents a challenging and under‐developed class of transformations that is of significant potential utility, including in the synthesis of lipophilic active pharmaceutical ingredients. Herein, we report that a new, air‐stable Ni(II) pre‐catalyst incorporating the optimized ancillary ligand PhPAd‐DalPhos enables such transformations of (hetero)aryl chloride, bromide, and tosylate electrophiles to be carried out for the first time with substrate scope rivalling that achieved using state‐of‐the‐art Pd catalysts, including room temperature cross‐couplings of (hetero)aryl chlorides that are unprecedented for any catalyst (Pd, Ni, or other). 相似文献
993.
Khaled Cheaib M. Qadri E. Mubarak Katell Snchal‐David Christian Herrero Rgis Guillot Martin Clmancey Jean‐Marc Latour Sam P. deVisser Jean‐Pierre Mahy Frdric Banse Frdric Avenier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(3):864-868
We demonstrate that the devised incorporation of an alkylamine group into the second coordination sphere of an FeII complex allows to switch its reactivity with H2O2 from the usual formation of FeIII species towards the selective generation of an FeIV‐oxo intermediate. The FeIV‐oxo species was characterized by UV/Vis absorption and Mössbauer spectroscopy. Variable‐temperature kinetic analyses point towards a mechanism in which the heterolytic cleavage of the O?O bond is triggered by a proton transfer from the proximal to the distal oxygen atom in the FeII‐H2O2 complex with the assistance of the pendant amine. DFT studies reveal that this heterolytic cleavage is actually initiated by an homolytic O?O cleavage immediately followed by a proton‐coupled electron transfer (PCET) that leads to the formation of the FeIV‐oxo and release of water through a concerted mechanism. 相似文献
994.
Sam Benson Antonio Fernandez Nicole D. Barth Fabio deMoliner Mathew H. Horrocks C. Simon Herrington Jose Luis Abad Antonio Delgado Lisa Kelly Ziyuan Chang Yi Feng Miyako Nishiura Yuichiro Hori Kazuya Kikuchi Marc Vendrell 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(21):6985-6989
The transport and trafficking of metabolites are critical for the correct functioning of live cells. However, in situ metabolic imaging studies are hampered by the lack of fluorescent chemical structures that allow direct monitoring of small metabolites under physiological conditions with high spatial and temporal resolution. Herein, we describe SCOTfluors as novel small‐sized multi‐colored fluorophores for real‐time tracking of essential metabolites in live cells and in vivo and for the acquisition of metabolic profiles from human cancer cells of variable origin. 相似文献
995.
Dr. Pravin Kumar Ankush Jagtap Dr. Sam Asami Claudia Sippel Prof. Dr. Ville R. I. Kaila Prof. Dr. Felix Hausch Prof. Dr. Michael Sattler 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9529-9533
The recently discovered SAFit class of inhibitors against the Hsp90 co‐chaperone FKBP51 show greater than 10 000‐fold selectivity over its closely related paralogue FKBP52. However, the mechanism underlying this selectivity remained unknown. By combining NMR spectroscopy, biophysical and computational methods with mutational analysis, we show that the SAFit molecules bind to a transient pocket in FKBP51. This represents a weakly populated conformation resembling the inhibitor‐bound state of FKBP51, suggesting conformational selection rather than induced fit as the major binding mechanism. The inhibitor‐bound conformation of FKBP51 is stabilized by an allosteric network of residues located away from the inhibitor‐binding site. These residues stabilize the Phe67 side chain in a dynamic outward conformation and are distinct in FKBP52, thus rationalizing the basis for the selectivity of SAFit inhibitors. Our results represent a paradigm for the selective inhibition of transient binding pockets. 相似文献
996.
Calum T. J. Ferguson Niklas Huber Katharina Landfester Kai A. I. Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10677-10681
Selective activation of photocatalysts under constant light conditions has recently been targeted to produce multi‐responsive systems. However, controlled activation, with easy recovery of the photocatalysts, induced by external stimuli remains a major challenge. Mimicking the responsiveness of biological systems to multiple triggers can offer a promising solution. Herein, we report dual‐responsive polymer photocatalysts in the form of nanogels consisting of a cross‐linked poly‐N‐isopropylacrylamide nanogel, copolymerised with a photocatalytically active monomer. The dual‐responsive polymer nanogels undergo a stark decrease in diameter with increasing temperature, which shields the photocatalytic sites, decreasing the activity. Temperature‐dependent photocatalytic formation of NAD+ in water demonstrates the ability to switch photocatalysis on and off. Moreover, the photocatalysed syntheses of several fine chemicals were carried out to demonstrate the utility of the designed material. 相似文献
997.
R. Matthew Ferguson Kannan M. Krishnan 《Journal of magnetism and magnetic materials》2009,321(10):1548-1551
Magnetic particle imaging (MPI) is a powerful new research and diagnostic imaging platform that is designed to image the amount and location of superparamagnetic nanoparticles in biological tissue. Here, we present mathematical modeling results that show how MPI sensitivity and spatial resolution both depend on the size of the nanoparticle core and its other physical properties, and how imaging performance can be effectively optimized through rational core design. Modeling is performed using the properties of magnetite cores, since these are readily produced with a controllable size that facilitates quantitative imaging. Results show that very low detection thresholds (of a few nanograms Fe3O4) and sub-millimeter spatial resolution are possible with MPI. 相似文献
998.
The widely used traditional massless isolator model is only valid at relatively low frequencies. In this paper two classes of distributed parameter isolator, non-dispersive and dispersive, which are valid over a wide range of frequencies, are studied and compared. The important characteristics of such distributed parameter isolators in isolating a mass are given, as are the parameters which control the isolator performance at various frequencies. The theoretical findings for one distributed parameter isolator are validated experimentally using a helical spring, as an example of a non-dispersive isolator. 相似文献
999.
Bi-Hamiltonian structures involving Hamiltonian operators of degree 2 are studied. Firstly, pairs of degree 2 operators are considered in terms of an algebra structure on the space of 1-forms, related to so-called Fermionic Novikov algebras. Then, degree 2 operators are considered as deformations of hydrodynamic type Poisson brackets. 相似文献
1000.
Jackie L. Gartner-Schmidt Clark A. Rosen Nandhakumar Radhakrishnan Berrylin J. Ferguson 《Journal of voice》2008,22(3):333-338
This study was to present an odor provocation/challenge test for laryngeal hypersensitivity in a suspected odor induced dysphonic patient. The second aim was to rule out secondary gain from organic laryngeal hypersensitivity. Two steps were taken for this purpose. First, because the evaluation of hypersensitivity may be affected by the perception of odor, the study investigated laryngeal hypersensitivity during nasal and oral breathing separately to disentangle possible cognitive reactions to odors. Second, a healthy control (HC) participant was used with the identical testing protocol for nasal breathing to minimize unbiased results. The HC's response to nasal breathing of the odors showed no response to all the stimuli. The participant with possible secondary gain issues responded differently to the odors when presented nasally versus orally. Oral breathing showed less severe and less frequent laryngeal hypersensitive reactions. This suggests that laryngeal hypersensitivity was either due to the odor, cognitive information, sensory changes in olfaction leading to psychological conditioning, or for any possible secondary gain. Hence, it is difficult to indicate the precise reason (cause and effect) for the participant's laryngeal hypersensitivity; however, this study describes the first structured, controlled, repeatable, and randomized design to investigate odor induced laryngeal hypersensitivity and decipher possible secondary gain from true laryngeal hypersensitivity. 相似文献