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71.
72.
Albert J. R. Heck Leo J. de Koning Nice M. M. Nibbering 《Journal of the American Society for Mass Spectrometry》1991,2(6):453-458
Results of a Fourier transform-ion cyclotron resonance study are reported concerning the reactivity of protonated perdeuteromethane and deuteronated methane, generated under varying pressure conditions in an external chemical ionization ion source, toward ammonia. The competition between proton and deuteron transfer from both protonated perdeuteromethane and deuteronated methane to ammonia exhibits chemically distinguishable hydrogens. The chemical behavior of protonated methane appears to be compatible with the theoretically predicted stable structure with CS symmetry, involving a three-center two-electron bond associating two hydrogens and the carbon atom. Interconversion of this structure due to exchange between one of these hydrogens and one of the three remaining hydrogens appears to be a fast process that is induced by interactions with the chemical ionization gas. 相似文献
73.
This paper discusses the molecular design of selected examples of structural units containing taper shaped exo-receptors and various crown ether, oligooxyethylenic, and H-bonding based endo-receptors, which self-assemble into cylindrical channel-like architectures via principles resembling those of tobacco mosaic virus (TMV). The ability of these structural units to self- assemble via a delicate combination of exo-and endo-recognition processes will be presented. A comparison between various supramolecular (generated via H-bonding, ionic, and electrostatic interactions) and molecular “polymer backbones” will be made. The present limitations concerning the ability to engineer the structural parameters of these supramolecular channel-like architectures and some possible novel material functions derived from them will be briefly mentioned. 相似文献
74.
ZrIV and TaV Complexes with Methano‐Bridged Bis(aryloxy) Ligands The bis(aryloxy) ligand precursor compounds bis(2‐trimethylsiloxy‐5‐tbutylphenyl)methane (L–SiMe3) and its bromoderivative (2‐trimethylsiloxy‐3‐bromo‐5‐tbutylphenyl)(2′‐trimethylsiloxy‐5′‐tbutylphenyl)methane (LBr–SiMe3) are prepared in analogy to the corresponding calixarenes in excellent yields. X‐ray structure analysis for LBr–SiMe3: space group P21/c, a = 12.462(7), b = 10.466(6), c = 23.315(14) Å, β = 105.02(4)°, V = 2937(3) Å3, Z = 4. L–SiMe3 and LBr–SiMe3 react with ZrIV and TaV chlorides in very good yields forming di‐ and trinuclear complexes. From the reaction of CpZrCl3 with LBr–SiMe3 in the ratio of 3 : 2 a Zr3 complex ( 7 ) is obtained, with one LBr ligand only, which Zr atoms are bridged by a μ3‐oxygen. The X‐ray structure analysis of 7 (space group R 3, a = 33.23(6), c = 24.47(8) Å, V = 23405(128) Å3, Z = 18) additionally reveals that one phenolato oxygen atom of the LBr ligand is terminally bound to a distorted tetragonal‐pyramidal coordinated Zr atom, while the second phenolato oxygen atom of the LBr ligand forms a bridge to another Zr atom with a distorted octahedral coordination. The third Zr atom is also found in a distorted octahedral coordination mode. The reactions of L–SiMe3 and LBr–SiMe3 with CpTaCl4 and TaCl5 yield dinuclear Ta complexes with a bridging bis(aryloxy) ligand. NMR spectroscopic data point out that the coordination of the bis(aryloxy) ligands in the Ta complexes very much resembles that in the Zr3‐complex with one terminal and one bridging phenolato oxygen atom. The Zr3 and the Ta complexes LBrTa2Cp2Cl6 and LTa2Cl8 were tested with respect to their catalytic properties in olefin polymerisation reactions in the presence of MAO. 相似文献
75.
76.
van den Bremer ET Keeble AH Kleanthous C Heck AJ 《Chemical communications (Cambridge, England)》2005,(9):1137-1139
Mass spectrometric and calorimetric data reveal that phosphate ion binding to the active site of colicin E9 DNase is delicately regulated by concomitant binding of specific transition metal ions. 相似文献
77.
Häfele A Heck B Hippler T Kawai T Kohn P Strobl G 《The European physical journal. E, Soft matter》2005,16(2):217-224
Dilatometric and X-ray scattering experiments of the
crystallization kinetics of a sample of poly(ethylene-co-octene)
show pronounced melt memory effects, i.e., the shapes of isotherms
and characteristic times vary systematically with the temperature
of the melt prior to cooling to the crystallization temperature.
The temperature range of the effect is limited; crystallization
kinetics remains constant below a melt temperature Tm
l and above a melt temperature Tmh and varies
only in-between. Analysis shows that the melt memory effect is
caused by a variation of the characteristic time of a first order
crystallization process. The process can be assigned to the
in-filling of crystallites into objects of a previously generated
precursor structure. 相似文献
78.
79.
A new cryptate incorporating an unsymmetrical arch as 6-methyl-2-[3-(methyl)pyrazol-1′-yl]pyridine has been obtained in a good yield. The effect of the dissymmetry introduced by the pyrazole moiety on the corresponding Eu(III), Tb(III) and Sm(III) complex fluorescence behavior is discussed. 相似文献
80.
Seven upper-rim fully tethered cyclodextrins (URFT-CDs) have been synthesised in a good average coupling yield using the one-step "phosphine imide" approach and their metal complexation behaviour with lanthanides and transition metals was explored. We observed that the A-TE-E light conversion process (antennae effect) occurs in the URFT-CD lanthanide complexes. A molecular redox switch based on the corresponding iron complexes is also reported. A reversible intramolecular translocation of the FeII and FeIII ions, between two distinct binding cavities has been monitored spectroscopically and achieved by chemical triggering. Finally, a negative allosteric control of ion recognition through the formation of a CD pseudocryptand is discussed. 相似文献