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181.
McKeown BA Gonzalez HE Friedfeld MR Gunnoe TB Cundari TR Sabat M 《Journal of the American Chemical Society》2011,133(47):19131-19152
Cationic platinum(II) complexes [((t)bpy)Pt(Ph)(L)](+) [(t)bpy =4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC(5)F(5), or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkyl arene products is achieved after 4 h at 120 °C. Catalyst efficiency for ethylene hydrophenylation is diminished only slightly under aerobic conditions. Mechanistic studies support a reaction pathway that involves ethylene coordination to Pt(II), insertion of ethylene into the Pt-phenyl bond, and subsequent metal-mediated benzene C-H activation. Studies of stoichiometric benzene (C(6)H(6) or C(6)D(6)) C-H/C-D activation by [((t)bpy)Pt(Ph-d(n))(THF)](+) (n = 0 or 5) indicate a k(H)/k(D) = 1.4(1), while comparative rates of ethylene hydrophenylation using C(6)H(6) and C(6)D(6) reveal k(H)/k(D) = 1.8(4) for the overall catalytic reaction. DFT calculations suggest that the transition state for benzene C-H activation is the highest energy species along the catalytic cycle. In CD(2)Cl(2), [((t)bpy)Pt(Ph)(THF)][BAr'(4)] [Ar' = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [((t)bpy)Pt(CH(2)CH(2)Ph)(η(2)-C(2)H(4))][BAr'(4)] with k(obs) = 1.05(4) × 10(-3) s(-1) (23 °C, [C(2)H(4)] = 0.10(1) M). In the catalytic hydrophenylation of ethylene, substantial amounts of diethylbenzenes are produced, and experimental studies suggest that the selectivity for the monoalkylated arene is diminished due to a second aromatic C-H activation competing with ethylbenzene dissociation. 相似文献
182.
Klaysom C Moon SH Ladewig BP Lu GQ Wang L 《Journal of colloid and interface science》2011,363(2):431-439
A new type of nanocomposite ion-exchange membranes containing sulfonated polyethersulfone (sPES) polymer matrix and sulfonated surface-functionalized mesoporous silica (SS) inorganic fillers was prepared. Various characterizations revealed that the addition of inorganic fillers with different shapes had a significant influence on the membrane structure. The mesoporous inorganic fillers not only created extra pore and water channels, assisting the ionic migration and improving conductivity of the composites, but also provided additional fixed charge groups upon surface modification. This allows the Donnan exclusion to work effectively and thus improve the selectivity of membranes. It was proved that the incorporation of appropriate amount of SS additive could significantly improve the conductivity (up to 20 folds) and permselectivity (about 14%) of the sPES membranes. The performance of these newly developed membranes in desalination by electrodialysis was comparable with that of a commercial membrane (FKE). 相似文献
183.
184.
Martin Hedegaard Christian Matth?us S?ren Hassing Christoph Krafft Max Diem J��rgen Popp 《Theoretical chemistry accounts》2011,130(4-6):1249-1260
A detailed comparison of six multivariate algorithms is presented to analyze and generate Raman microscopic images that consist of a large number of individual spectra. This includes the segmentation algorithms for hierarchical cluster analysis, fuzzy C-means cluster analysis, and k-means cluster analysis and the spectral unmixing techniques for principal component analysis and vertex component analysis (VCA). All algorithms are reviewed and compared. Furthermore, comparisons are made to the new approach N-FINDR. In contrast to the related VCA approach, the used implementation of N-FINDR searches for the original input spectrum from the non-dimension reduced input matrix and sets it as the endmember signature. The algorithms were applied to hyperspectral data from a Raman image of a single cell. This data set was acquired by collecting individual spectra in a raster pattern using a 0.5-??m step size via a commercial Raman microspectrometer. The results were also compared with a fluorescence staining of the cell including its mitochondrial distribution. The ability of each algorithm to extract chemical and spatial information of subcellular components in the cell is discussed together with advantages and disadvantages. 相似文献
185.
McGillen MR Ghalaieny M Percival CJ 《Physical chemistry chemical physics : PCCP》2011,13(23):10965-10969
The rates of ozonolysis of a suite of terminal alkenes ranging from C(8-14) are determined in the gas phase at an elevated temperature of 395.9 ± 1.2 K and a pressure of ~650 Torr using the EXTreme RAnge chamber (EXTRA). Rates are found to be invariant with carbon number, whilst literature measurements conducted under ambient conditions exhibited an increase in rate coefficient after 10 carbon atoms. These earlier findings appear to contradict the intuitive notion that the inductive effect is a short-range process operating over a maximum distance of a few carbon atoms. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution. 相似文献
186.
Four M Riehl D Mongin O Blanchard-Desce M Lawson-Daku LM Moreau J Chauvin J Delaire JA Lemercier G 《Physical chemistry chemical physics : PCCP》2011,13(38):17304-17312
In this article, the synthesis of a novel high-conjugated ligand and its corresponding Ru(II) complex PTFTF:Ru is reported, along with the linear and nonlinear optical characterizations. Two-photon absorption based optical power limiting properties (OPL), especially in the near infrared, are described and compared to those of the analogous complexes previously published. Combined with a preliminary theoretical approach, this allows us to highlight several key parameters for OPL optimization in such molecular systems and more particularly the spectral overlap between TPA and excited-state absorption. 相似文献
187.
A methodology is developed for the numerical solution to the sample-based optimal transport and Wasserstein barycenter problems. The procedure is based on a characterization of the barycenter and of the McCann interpolants that permits the decomposition of the global problem under consideration into various local problems where the distance among successive distributions is small. These local problems can be formulated in terms of feature functions and shown to have a unique minimizer that solves a nonlinear system of equations. Both the theoretical underpinnings of the methodology and its practical implementation are developed, and illustrated with synthetic and real data sets. © 2019 Wiley Periodicals, Inc. 相似文献
188.
Derek Booth Jack Burkart Xiaodong Cao Max Hallgren Zachary Munro Jason Snyder Tom Stone 《分析论及其应用》2019,35(2):192-204
This paper will develop a Li-Yau-Hamilton type differential Harnack estimate for positive solutions to the Newell-Whitehead-Segel equation on R^n.We then use our LYH-differential Harnack inequality to prove several properties about positive solutions to the equation,including deriving a classical Harnack inequality and characterizing standing solutions and traveling wave solutions. 相似文献
189.
In this work, we readdress the photoelectron spectra of the HM(CO)5, (M=Mn, Re) carbonyl complexes by applying four-component Fock-space coupled cluster (FSCC) methods for their calculation in order to extend earlier studies based on less demanding approaches. The final-state characterisation was based on group theoretical considerations of the contributing orbitals and allowed for an unambiguous assignment. Energy level diagrams show the effect of spin–orbit (SO) coupling starting from scalar relativistic results and for the heavy representative HRe(CO)5 nonadditivity effects of SO and electron correlation can be observed requiring a consistent treatment of both contributions. 相似文献
190.
Afshin Nabiyan Johannes Bernhard Max Dr. Christof Neumann Magdalena Heiland Prof. Dr. Andrey Turchanin Prof. Dr. Carsten Streb Prof. Dr. Felix Helmut Schacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):16924-16929
An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO2 core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO2). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO2 core. This resulted in high visible-light-driven H2 generation. The enhanced light-driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO2 was possible by introducing [Mo3S13]2− cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species. 相似文献