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821.
    
Core–shell polymer supports with different morphological features and compositions are prepared through combined suspension and emulsion polymerizations. It is shown that proper manipulation of the divinylbenzene (DVB) feed content allows for maximization of specific areas, porosities, and mechanical resistances. Additionally, it is shown that feeding of previously prepared miniemulsions leads to core–shell particles with smaller specific areas, due to less efficient coating of the cores. Particularly, the combined manipulation of polymerization times and DVB feed compositions allows for production of particles with pronounced specific area (50 m2 g?1) and porosity (0.30 cm3 g?1). Produced core–shell polymer particles are employed as supports for the immobilization of lipase B from Candida antarctica, and the obtained enzymatic activities for both hydrolysis (A hyd) and esterification (A est) reactions are very high (A hyd = 34.7 ± 3.8 U/g; A est = 3564.6 ± 581 U/g), even when compared to activities obtained using the reference commercial biocatalyst Novozym 435 (A hyd = 7.6 ± 1.8 U/g, A est = 2384.7 ± 307.2 U/g). Finally, biocatalysts prepared with the core–shell supports present higher enzymatic activities than biocatalysts prepared with supports of higher specific area obtained through conventional emulsion polymerizations, indicating that the porous structure of the shell can be beneficial for the immobilization and activity of the enzymes.  相似文献   
822.
    
As part of our effort to improve our understanding of aziridination mechanism, we used tetra substitution of a diphenol ligand to modify the redox properties of corresponding Fe complexes. This allowed us to confirm that aziridination catalysis by Fe-based complexes is governed by electron affinity of the active species and further show that it correlates with the FeIII/FeII redox potential.  相似文献   
823.
    
Mixed‐ligands hydride complexes [RuHCl(CO)(PPh3)2{P(OR)3}] ( 2 ) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh3)3] ( 1 ) to react with an excess of phosphites P(OR)3 in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(κ1‐NH2NHR1)(PPh3)2{P(OR)3}]BPh4 ( 3 , 4 ) (R1 = H, CH3). Diethylcyanamide derivatives [RuCl(CO)(N≡CNEt2)(PPh3)2{P(OR)3}]BPh4 ( 5 ) were also prepared by reacting 2 first with HOTf and then with N≡CNEt2. The complexes were characterized spectroscopically and by X‐ray crystal structure determination of [RuHCl(CO)(PPh3)2{P(OEt)3}] ( 2b ).  相似文献   
824.
    
Hybrid type I PKS/NRPS biosynthetic pathways typically proceed in a collinear manner wherein one molecular building block is enzymatically incorporated in a sequence that corresponds to gene arrangement. In this work, genome mining combined with the use of a fluorogenic azide‐based click probe led to the discovery and characterization of vatiamides A–F, three structurally diverse alkynylated lipopeptides, and their brominated analogues, from the cyanobacterium Moorea producens ASI16Jul14‐2. These derive from a unique combinatorial non‐collinear PKS/NRPS system encoded by a 90 kb gene cluster in which an upstream PKS cassette interacts with three separate cognate NRPS partners. This is facilitated by a series of promiscuous intermodule PKS‐NRPS docking motifs possessing identical amino acid sequences. This interaction confers a new type of combinatorial capacity for creating molecular diversity in microbial systems.  相似文献   
825.
Large-eddy simulations of the dispersion from scalar line sources at various locations within a fully developed turbulent channel flow at Re = uh/ν = 10,400 are presented. Both mean and fluctuating scalar quantities are compared with those from the single available set of experimental data (Lavertu and Mydlarski, J Fluid Mech 528:135–172, 2005) and differences are highlighted and discussed. The results are also discussed in the context of scalar dispersion in other kinds of turbulent flows, e.g. homogeneous shear-flow. Initial computations at a much lower Reynolds number are also reported and compared with the two available direct numerical simulation data sets.  相似文献   
826.
827.
The reactions of secondary alicyclic amines with the title substrate (PDTC) are subjected to a kinetic study in 44 wt.% aqueous ethanol, 25.0°C, ionic strength 0.2 M (KCl). Pseudo-first-order rate coefficients (kobs) are found under amine excess. Linear plots of [N]/kobs against 1/[N], where N is the free amine, are obtained for the reactions with piperidine, piperazine, 1-(2-hydroxyethyl)piperazine, and morpholine. The reaction with 1-formylpiperazine exhibits a linear plot of kobs against [N]2. These results are interpreted through a mechanism consisting of two tetrahedral intermediates: a zwitterionic ( T ±) and an anionic ( T ?), where the amine catalyzed proton transfer from T ± to T ? is partially rate determining for the four former reactions and is fully rate determining for the reaction of 1-formylpiperazine. The rate microcoefficients involved in the reaction scheme are either determined experimentally or estimated. Comparison with the corresponding microcoefficients reported for the same reactions in water reveals that the rate coefficient for formation of T ± from reactants (k1) is smaller and that for the reversal of this (k?1) is larger in aqueous ethanol compared to water, in agreement with the expected structure of the corresponding transition state. Bronsted-type plots are obtained for k1, k?1, and K1 (=k1/k?1) with slopes ca. 0.4, ?0.6, and 1.0, respectively. Comparison of the present stepwise reactions with the concerted ones found in the same aminolysis of O-ethyl 2,4,6,-(trinitrophenyl) dithiocarbonate indicates that T ± is so destabilized by the change of PhS by the 2,4,6-trinitrobenzenethio group that T ± no longer exists and becomes a transition state. © 1995 John Wiley & Sons, Inc.  相似文献   
828.
829.
Controlling the surface chemistry of oxide systems has emerged an effective tool to obtain desirable nanostructures and macro properties. A relatively simple way to achieve this is by using dopants that are prone to segregate to the surfaces of the powders. In this work, we delineate the effect of Mg and Fe on SnO2 nanopowders focusing on the surface modifications caused by surface segregation. The effects of increasing the temperature of calcinations are particularly addressed to evaluate the surface modifications at high temperatures. The powders were studied by infrared spectroscopy, zeta potential measurements, X-ray diffraction, and specific surface area measurements. Since sintering is a high-temperature process strongly dependent on surface characteristics, we drawn a relationship between the final densities after sintering and the surface chemistry of the doped powders. Doped SnO2 pellets were sintered to over 95% of the theoretical density within a few seconds (fast firing) when significant surface modifications were observed.  相似文献   
830.
This work reports the role of alpha particles generated by Americium (241Am) stripes placed inside the discharge channel in providing a bias ionized background plasma before, during, and after the discharge of the N2 TE UV laser (337.1 nm) circuit. The enhancement in stimulated radiation output characteristics in terms of gas pressure, charging voltage, and pulse width, with and without alpha particles, are shown. The increased laser yield is interpreted qualitatively through plasma impedance in the discharge circuit. PACS 42.60.By; 42.60.Lh  相似文献   
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