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排序方式: 共有138条查询结果,搜索用时 990 毫秒
61.
Zhou Z Steigerwald M Hybertsen M Brus L Friesner RA 《Journal of the American Chemical Society》2004,126(11):3597-3607
All-electron static and time-dependent DFT electronic calculations, with complete geometrical optimization, are performed on tubular molecules up to C(210)H(20) that are finite sections of the (5,5) metallic single wall carbon nanotube with hydrogen termination at the open ends. We find pronounced C-C bond reconstruction at the tube ends; this initiates bond alternation that propagates into the tube centers. For the especially low band gap molecules C(120)H(20), C(150)H(20), and C(180)H(20), alternation increases, and a second nearly isoenergic structural isomer of different alternation is found. A small residual C-C bond alternation and band gap may be present in the infinite tube. The van Hove band gap forms quickly with length, while the metallic Fermi point (at the crossing of linear bands) forms very slowly with length. There are no end-localized states at energies near the Fermi energy. The HOMO-LUMO gap and the lowest singlet excited state, whose energies show a periodicity with length as previously calculated, are optically forbidden. However, each molecule shows an intense visible "charge transfer" transition, not present in the infinite tube, whose energy varies smoothly with length; this transition should be an identifying signature for these molecules. The static axial polarizability per unit length increases rapidly with N as the "charge transfer" transition moves into the infrared; this indicates increasing metallic character. However, the ionization potential, electron affinity, chemical hardness, and relative energetic stability all show the length periodicity seen in the HOMO-LUMO gap, in contrast to the optical "charge transfer" transition and the static axial polarizability. These periodicities, due to a one-dimensional quantum size effect as originally modeled by Coulson in 1938, nevertheless cancel in the calculated Fermi energy, which varies smoothly toward a predicted bulk work function near 3.9 eV. A detailed study of C(190)H(20) with up to eight extra electrons or holes shows the total energy is closely fit by a simple classical charging model, as is commonly applied to metallic clusters. 相似文献
62.
Smith MB Page K Siegrist T Redmond PL Walter EC Seshadri R Brus LE Steigerwald ML 《Journal of the American Chemical Society》2008,130(22):6955-6963
We have investigated the paraelectric-to-ferroelectric phase transition of various sizes of nanocrystalline barium titanate (BaTiO3) by using temperature-dependent Raman spectroscopy and powder X-ray diffraction (XRD). Synchrotron X-ray scattering has been used to elucidate the room temperature structures of particles of different sizes by using both Rietveld refinement and pair distribution function (PDF) analysis. We observe the ferroelectric tetragonal phase even for the smallest particles at 26 nm. By using temperature-dependent Raman spectroscopy and XRD, we find that the phase transition is diffuse in temperature for the smaller particles, in contrast to the sharp transition that is found for the bulk sample. However, the actual transition temperature is almost unchanged. Rietveld and PDF analyses suggest increased distortions with decreasing particle size, albeit in conjunction with a tendency to a cubic average structure. These results suggest that although structural distortions are robust to changes in particle size, what is affected is the coherency of the distortions, which is decreased in the smaller particles. 相似文献
63.
Photovoltage mechanism for room light conversion of citrate stabilized silver nanocrystal seeds to large nanoprisms 总被引:2,自引:0,他引:2
Wu X Redmond PL Liu H Chen Y Steigerwald M Brus L 《Journal of the American Chemical Society》2008,130(29):9500-9506
We investigate the photoconversion of aqueous 8 nm Ag nanocrystal seeds into 70 nm single crystal plate nanoprisms. The process relies on the excitation of Ag surface plasmons. The process requires dioxygen, and the transformation rate is first-order in seed concentration. Although citrate is necessary for the conversion, and is consumed, the transformation rate is independent of citrate concentration. We propose a mechanism that accounts for these features by coupling the oxidative etching of the seed and the subsequent photoreduction of aqueous Ag(+). The reduced Ag deposits onto a Ag prism of specific size that has a cathodic photovoltage resulting from plasmon "hot hole" citrate photo-oxidation. This photovoltage mechanism also explains recent experimental results involving single and dual wavelength irradiation and the core/shell synthesis of Ag layers on Au seeds. 相似文献
64.
Carnes M Buccella D Siegrist T Steigerwald ML Nuckolls C 《Journal of the American Chemical Society》2008,130(43):14078-14079
Here we describe the metathesis reactions of a strained eight-membered ring that contains both alkene and alkyne functionality. We find that the alkyne metathesis catalyst produces polymer through a ring-opening alkyne metathesis reaction that is driven by the strain release from the monomer. The strained monomer provides unusual reactivity with ruthenium-based alkene metathesis catalysts. We isolate a discrete trimeric species a Dewar benzene derivative that is locked in this form through an unsaturated cyclophane strap. 相似文献
65.
66.
Summary A preparation method is described for analysing size classified rain drops by SEM (scanning electron microscopy), equipped with an energy-dispersive detection system. The concentration is determined by addition of an internal standard. This allows the quantitative analysis of samples with a volume of 2 l and a concentration of 1 g/l. The time of measurement is 100 s.Dedicated to Professor Dr. V. Krivan on the occasion of his 60th birthday 相似文献
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69.
Noah J. Tremblay Alon A. Gorodetsky Dr. Marshall P. Cox Theanne Schiros Dr. Bumjung Kim Rachel Steiner Zachary Bullard Aaron Sattler Woo‐Young So Dr. Yoshimitsu Itoh Dr. Michael F. Toney Dr. Hirohito Ogasawara Dr. Arthur P. Ramirez Prof. Ioannis Kymissis Dr. Michael L. Steigerwald Dr. Colin Nuckolls Prof. 《Chemphyschem》2010,11(4):799-803
70.
Nafisah Al‐Rifai Hannelore Rücker Dr. Sabine Amslinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15384-15395
Thiol‐mediated processes play a key role to induce or inhibit inflammation proteins. Tailoring the reactivity of electrophiles can enhance the selectivity to address only certain surface cysteines. Fourteen 2′,3,4,4′‐tetramethoxychalcones with different α‐X substituents (X=H, F, Cl, Br, I, CN, Me, p‐NO2‐C6H4, Ph, p‐OMe‐C6H4, NO2, CF3, COOEt, COOH) were synthesized, containing the potentially electrophilic α,β‐unsaturated carbonyl unit. The assessment of their reactivity as electrophiles in thia‐Michael additions with cysteamine shows a change in the reactivity of more than six orders of magnitude. Moreover, a clear correlation between their reactivity and an influence on the inflammation proteins heme oxygenase‐1 (HO‐1) and the inducible NO synthase (iNOS) is demonstrated. As the biologically most active compound, the α‐CF3‐chalcone is shown to inhibit the NO production in RAW264.7 mouse macrophages in the nanomolar range. 相似文献