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31.
32.
A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived
Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction
of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian
blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme
is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated. 相似文献
33.
Alexander M. Khenkin Dr. Irena Efremenko Dr. Lev Weiner Dr. Jan M. L. Martin Prof. Ronny Neumann Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(4):1356-1364
A polyoxometalate of the Keggin structure substituted with RuIII, 6Q5[RuIII(H2O)SiW11O39] in which 6Q=(C6H13)4N+, catalyzed the photoreduction of CO2 to CO with tertiary amines, preferentially Et3N, as reducing agents. A study of the coordination of CO2 to 6Q5[RuIII(H2O)SiW11O39] showed that 1) upon addition of CO2 the UV/Vis spectrum changed, 2) a rhombic signal was obtained in the EPR spectrum (gx=2.146, gy=2.100, and gz=1.935), and 3) the 13C NMR spectrum had a broadened peak of bound CO2 at 105.78 ppm (Δ1/2=122 Hz). It was concluded that CO2 coordinates to the RuIII active site in both the presence and absence of Et3N to yield 6Q5[RuIII(CO2)SiW11O39]. Electrochemical measurements showed the reduction of RuIII to RuII in 6Q5[RuIII(CO2)SiW11O39] at ?0.31 V versus SCE, but no such reduction was observed for 6Q5[RuIII(H2O)SiW11O39]. DFT‐calculated geometries optimized at the M06/PC1//PBE/AUG‐PC1//PBE/PC1‐DF level of theory showed that CO2 is preferably coordinated in a side‐on manner to RuIII in the polyoxometalate through formation of a Ru? O bond, further stabilized by the interaction of the electrophilic carbon atom of CO2 to an oxygen atom of the polyoxometalate. The end‐on CO2 bonding to RuIII is energetically less favorable but CO2 is considerably bent, thus favoring nucleophilic attack at the carbon atom and thereby stabilizing the carbon sp2 hybridization state. Formation of a O2C–NMe3 zwitterion, in turn, causes bending of CO2 and enhances the carbon sp2 hybridization. The synergetic effect of these two interactions stabilizes both Ru–O and C–N interactions and probably determines the promotional effect of an amine on the activation of CO2 by [RuIII(H2O)SiW11O39]5?. Electronic structure analysis showed that the polyoxometalate takes part in the activation of both CO2 and Et3N. A mechanistic pathway for photoreduction of CO2 is suggested based on the experimental and computed results. 相似文献
34.
Growth of metal-organic frameworks on polymer surfaces 总被引:1,自引:0,他引:1
Centrone A Yang Y Speakman S Bromberg L Rutledge GC Hatton TA 《Journal of the American Chemical Society》2010,132(44):15687-15691
Polymer substrates have been functionalized with a MOF material (MIL-47) synthesized directly on polyacrylonitrile using in situ microwave irradiation. The growth of MIL-47 on these substrates was studied as a function of microwave irradiation time using scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The conversion of nitrile to carboxylic acid groups on the PAN surface was necessary for the growth of MIL-47 on the substrate. MIL-47 crystals grew over time at the expense of a related disordered precursor phase, which lacks the long-range order of MIL-47. This work paves the way for the development of a new class of hybrid MOF-polymer materials that will extend the applications of MOFs to fields such as membrane separations, filtration, and protective textiles. 相似文献
35.
Churakov AV Prikhodchenko PV Lev O Medvedev AG Tripol'skaya TA Vener MV 《The Journal of chemical physics》2010,133(16):164506
The crystal structure of NH(4)(+)OOH(-) is determined from single-crystal x-ray data obtained at 150 K. The crystal belongs to the space group P2(1)/c and has four molecules in a unit cell. The structure consists of discrete NH(4)(+) and OOH(-) ions. The OOH(-) ions are linked by short hydrogen bonds (2.533 A?) to form parallel infinite chains. The ammonium ions form links between these chains (the N?O distances vary from 2.714 to 2.855 A?) giving a three-dimensional network. The harmonic IR spectrum and H-bond energies are computed at the Perdew-Burke-Ernzerhof (PBE)/6-31G(??) level with periodic boundary conditions. A detailed analysis of the shared (bridging) protons' dynamics is obtained from the CPMD simulations at different temperatures. PBE functional with plane-wave basis set (110 Ry) is used. At 10 K the shared proton sits near the oxygen atom, only a few proton jumps along the chain are detected at 70 K while at 270 K numerous proton jumps exist in the trajectory. The local-minimum structure of the space group Cc is localized. It appears as a result of proton transfer along a chain. This process is endothermic (~2?kJ/mol) and is described as P2(1)/c?2Cc. The computed IR spectrum at 10 K is close to the harmonic one, the numerous bands appear at 70 K while at 270 K it shows a very broad absorption band that covers frequencies from about 1000 to 3000?cm(-1). The advantages of the NH(4)(+)OOH(-) crystal as a promising model for the experimental and DFT based molecular dynamics simulation studies of proton transfer along the chain are discussed. 相似文献
36.
37.
A new family of copper ligand-exchange selectors, L- or D-β-amino alcohols, is employed for the chiral separation of D,L-dansyl-amino acids, unmodified amino acid racemates, phenylalanine and tryptophan, and β-blocker L,D-propranolol by SDS-micellar electrokinetic chromatography and by electrophoretic chromatography in a low molecular weight organogel (LMOG)-filled capillary. The LMOG comprised a self-assembled fibrillar gel of trans-(1S,2S)-1,2-bis-(dodecylamido) cyclohexane in methanol. The di-L-valinol-copper complex exhibited the best performance on LMOG-CE compared with all other β-amino alcohol-copper selectors. The dependence of chiral resolution on the pH*, the ratio between the copper and the L-valinol ligand and the concentration of added selector complex in the run buffer were investigated revealing a marked difference between the activity of the copper-valinol and the previously studied copper-valine selector. The optimal separation conditions were achieved using a 2:1 valinol/copper ratio, in accordance with the 2:1 structure of the complex, which was proven by single crystal and powder X-ray diffractions and by elemental analysis. Unlike the copper-valine selectors that could be used only under acidic conditions (pH* 3.5), the copper-valinol selectors could be used under near-neutral conditions and even at pH* 9.1. A comparison between SDS-micellar electrokinetic chromatography and LMOG-CE under otherwise identical conditions revealed a significant superior separation on the LMOG-filled capillaries. 相似文献
38.
Cangelosi VM Carter TG Crossland JL Zakharov LN Johnson DW 《Inorganic chemistry》2010,49(21):9985-9992
A series of Group 15-containing homometallic (E(2)L(3), E = P, As, Sb, Bi) and heterometallic (AsSbL(3), AsBiL(3), PSbL(3)) supramolecular cryptands were prepared by the self-assembly of pnictogen halides with dithiolate ligand or by direct transmetalation from a heavier congener. Structural characterization by single crystal X-ray diffraction shows that the E-S bond distances and S-E-S bond angles are significantly affected by the identity of the pnictogen. (1)H NMR spectroscopy reveals that the homometallic cryptands are dynamic in solution: surprisingly one ligand "flips", perturbing the C(3) symmetry of the complex and giving a new asymmetric conformer. Density functional theory calculations were carried out on both the symmetric and the asymmetric conformations of the cryptands, and the energies were compared to those observed by NMR spectroscopy. It was found that the relative stability of the asymmetric cryptand to its symmetric conformer increases with increasing size of the Group 15 element. Finally, it is reported that if two metals are present during the self-assembly process, heterometallic cryptands form. These supramolecular cryptands are reminiscent of their organic analogues, but result from a self-assembly process rather than a stepwise synthesis. Surprisingly, they possess conformational isomerism and exhibit dynamic transmetalation in their reactivity which provides access to otherwise unattainable assemblies. 相似文献
39.
Yitzhak Wolanov Ovadia Lev Andrei V. Churakov Alexander G. Medvedev Vladimir M. Novotortsev Petr V. Prikhodchenko 《Tetrahedron》2010,66(27-28):5130-5133
Hydrogen peroxide is one of the most versatile oxidation reagents, still it has not fully been exploited by synthetic chemists since anhydrous (let alone pure) hydrogen peroxide requires hazardous preparation protocols. We have recently reported on the crystallization of serine and other amino acid perhydrates, thus paving the way for a new method for laboratory-scale production of anhydrous hydrogen peroxide solutions. Serine is insoluble in most organic solvents (e.g., methanol, ethyl acetate, and methyl acetate) that readily dissolve hydrogen peroxide. Moreover, since the adduct of hydrogen peroxide and serine is unstable in these organic solvents, crystalline serine perhydrate readily decomposes to give anhydrous solutions of hydrogen peroxide and crystalline precipitate of the amino acid. This procedure can then yield an anhydrous hydrogen peroxide solution in a single step. Moreover, filtration of the amino acid, and room temperature evaporation of the volatile solvent (e.g., methyl acetate), yields over 99% hydrogen peroxide. 相似文献
40.
Dr. Alexey A. Mikhaylov Dr. Alexander G. Medvedev Dr. Andrei V. Churakov Dmitry A. Grishanov Dr. Petr V. Prikhodchenko Prof. Dr. Ovadia Lev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):2980-2986
Tellurium–peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH4)4Te2(μ‐OO)2(μ‐O)O4(OH)2 ( 1 ) and (NH4)5Te2(μ‐OO)2(μ‐O)O5(OH)?1.28 H2O?0.72 H2O2 ( 2 ) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single‐crystal and powder X‐ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te2(μ‐OO)2(μ‐O)O4(OH)2]4?. The structure of 2 consists of an unsymmetrical [Te2(μ‐OO)2(μ‐O)O5(OH)]5? anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te2(μ‐OO)2(μ‐O) fragment with one μ‐oxo‐ and two μ‐peroxo bridging groups. 125Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3–40 %wt H2O2 and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium–peroxide coordination in any aqueous system and the first report of inorganic tellurium–peroxo complexes. General features common to all reported p‐block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates. 相似文献