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61.
Direct Synthesis of Highly Substituted Pyrroles and Dihydropyrroles Using Linear Selective Hydroacylation Reactions
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Manjeet K. Majhail Dr. Paul M. Ylioja Prof. Michael C. Willis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7879-7884
Rhodium(I) catalysts incorporating small bite‐angle diphosphine ligands, such as (Cy2P)2NMe or bis(diphenylphosphino)methane (dppm), are effective at catalysing the union of aldehydes and propargylic amines to deliver the linear hydroacylation adducts in good yields and with high selectivities. In situ treatment of the hydroacylation adducts with p‐TSA triggers a dehydrative cyclisation to provide the corresponding pyrroles. The use of allylic amines, in place of the propargylic substrates, delivers functionalised dihydropyrroles. The hydroacylation reactions can also be combined in a cascade process with a RhI‐catalysed Suzuki‐type coupling employing aryl boronic acids, providing a three‐component assembly of highly substituted pyrroles. 相似文献
62.
Dr. Mario Leypold Lukas Schuh Prof. Roland Fischer Dr. Ana Torvisco Prof. Michaela Flock Prof. Harald Stueger Dr. Michael Haas 《Angewandte Chemie (International ed. in English)》2017,56(28):8089-8093
Herein, we report on the first sila-aldol reaction, which emphasizes the tight connection between silicon and carbon chemistry. This novel synthetic method provides straightforward access to 2-oxahexasilabicyclo[3.2.1]octan-8-ide, a structurally complex silicon framework, in quantitative yield. Its structure was confirmed by NMR spectroscopy and X-ray crystallography, and it displays a distinctive charge-transfer transition. The complete mechanism of this highly selective rearrangement cascade is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this powerful silicon–carbon bond-forming strategy. 相似文献
63.
《Mendeleev Communications》2021,31(6):859-861
Various N-(pyridin-2-yl)acrylamides bearing 4H-chromene fragment were synthesized via the condensation of 4H-chromene-3-carbaldehydes and their fused analogues with 2H-pyrido[1,2-a]pyrimidine-2,4(3H)-diones employing NH4OAc/AcOH system. Possible mechanism of this hetero- domino reaction involves the consecutive Knoevenagel condensation, oxa-6v-electrocyclization, aza-6v-electrocyclic ring-opening, nucleophilic addition, retro-Alder-ene reaction and oxa-6v-electrocyclic ring-disclosure. 相似文献
64.
《Wave Motion》2017
An efficient approach for acoustic topology optimization to minimize the radiated sound power from a vibrating structure is described. The topology optimization is implemented by modifying the local stiffness at discrete locations on the surface of the structure. The radiated sound power level from the structure is directly chosen as the objective function to be minimized. A sensitivity analysis is then implemented to further optimize the layout of the locations of the modified local stiffness. To speed up the computational process, the radiated sound power is computed based on mapped acoustic radiation modes. To demonstrate the acoustic topology optimization using mapped acoustic radiation modes, the radiated sound power of a compressor housing is examined. Based on results from the numerical model, the local stiffness of a compressor housing was experimentally modified. Good agreement in sound power reduction obtained both numerically and experimentally was observed for the overall trend for the sound power levels as a function of one-third octave frequency bands. 相似文献
65.
Rational Design of an Ultrasensitive and Highly Selective Chemodosimeter by a Dual Quenching Mechanism for Cysteine Based on a Facile Michael‐Transcyclization Cascade Reaction
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Xiangmin Li Yongjun Zheng Hongjuan Tong Rui Qian Dr. Lin Zhou Prof. Dr. Guixia Liu Prof. Dr. Yun Tang Prof. Dr. Hao Li Prof. Dr. Kaiyan Lou Prof. Dr. Wei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9247-9256
Differentiation of biologically important thiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) is still a challenging task. Herein, we present a novel fluorescent chemodosimeter capable of selectively detecting Cys over other biothiols including Hcy and GSH and other amino acids by a facile thiol‐Michael addition/transcyclization rearrangement cascade click process. The unique transcyclization step is critical for the selectivity as a result of the kinetically favorable formation of a six‐membered ring with the Cys Michael adduct. Moreover, the probe adopts a distinctive dual quenching mechanism—photoinduced electron transfer (PET) and photoinduced intramolecular charge transfer (ICT) to deliver a drastic turn‐on fluorescence response only at the Cys‐selective transcylization step. The judicious selection of strong electron‐withdrawing naphthalimide fluorophore with maleimide group enhances the electrophilicity and thus reactivity for the cascade process leading to fast detection and ultrasensitivity with a detection limit of 2.0 nm (S/N=3). The probe has demonstrated its practical utility potential in Cys imaging in live cells. 相似文献
66.
The quest for higher peak focused intensities and better temporal contrast drives one to improve the design of all possible stages of the chirped pulse amplification (CPA) system. In this paper, we have analyzed the role of dispersion and spectral profile on the temporal shape and contrast ratio of the output pulse of a CPA system. The simulations indicate that an initial sech2 or a Gaussian pulse in the CPA system is best for a good contrast ratio. Incorporating a four-grating based pulse compressor in the CPA system improves the contrast as well as provides the flexibility to compensate the dispersion upto the fourth order. The simulations also detail the effect of spectral profile tailoring on the contrast ratio and peak power. 相似文献
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69.
Adrien Joseph 《Random Structures and Algorithms》2011,39(2):247-274
We provide information about the asymptotic regimes for a homogeneous fragmentation of a finite set. We establish a phase transition for the asymptotic behavior of the shattering times, defined as the first instants when all the blocks of the partition process have cardinality less than a fixed integer. Our results may be applied to the study of certain random split trees. © 2010 Wiley Periodicals, Inc. Random Struct. Alg., 39, 247‐274, 2011 相似文献
70.
Multi-Fractal Formalism for Quasi-Self-Similar Functions 总被引:1,自引:0,他引:1
The study of multi-fractal functions has proved important in several domains of physics. Some physical phenomena such as fully developed turbulence or diffusion limited aggregates seem to exhibit some sort of self-similarity. The validity of the multi-fractal formalism has been proved to be valid for self-similar functions. But, multi-fractals encountered in physics or image processing are not exactly self-similar. For this reason, we extend the validity of the multi-fractal formalism for a class of some non-self-similar functions. Our functions are written as the superposition of similar structures at different scales, reminiscent of some possible modelization of turbulence or cascade models. Their expressions look also like wavelet decompositions. For the computation of their spectrum of singularities, it is unknown how to construct Gibbs measures. However, it suffices to use measures constructed according the Frostman's method. Besides, we compute the box dimension of the graphs. 相似文献