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81.
82.
Perez-Mato JM Elcoro L Aroyo MI Katzke H Tolédano P Izaola Z 《Physical review letters》2006,97(11):115501
The phase of gallium GaII, with symmetry C222(1) and 104 atoms per unit cell, has been recently reported as an example of structural complexity under high pressure. It is shown here that this phase is a simple modulated distortion of an average structure of Fddd symmetry with all atoms structurally equivalent. The modulation can be described with only 4 parameters and satisfies symmetry properties described by a centrosymmetric superspace group. The structural distortion is dominated by a frozen transversal mode associated with a single irreducible representation of Fddd, with a wave vector on the line Q, at an edge of the Brillouin zone. The average structure can be related with an hcp configuration through simple sliding of hcp layers, reminiscent of the hcp-bcc Bürgers mechanism. 相似文献
83.
Yaping Zang Ilana Stone Michael S. Inkpen Fay Ng Tristan H. Lambert Colin Nuckolls Michael L. Steigerwald Xavier Roy Latha Venkataraman 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(45):16154-16158
A single‐molecule method has been developed based on the scanning tunneling microscope (STM) to selectively couple a series of aniline derivatives and create azobenzenes. The Au‐catalyzed oxidative coupling is driven by the local electrochemical potential at the nanostructured Au STM tip. The products are detected in situ by measuring the conductance and molecular junction elongation and compared with analogous measurements of the expected azobenzene derivatives prepared ex situ. This single‐molecule approach is robust, and it can quickly and reproducibly create reactions for a variety of anilines. We further demonstrate the selective synthesis of geometric isomers and the assembly of complex molecular architectures by sequential coupling of complementary anilines, demonstrating unprecedented control over bond formation at the nanoscale. 相似文献
84.
85.
Walter Strohmeier Hannelore Steigerwald Maria Lukács 《Journal of organometallic chemistry》1978,144(1):135-145
Catalytic activity of iridum complexes IrClCO[P(C6H11)3]2, IrCl[PPh3]3, IrHCO[PPh3]3 and IrH3[PPh3]3 in homogeneous hydrogenation of 17 typical unsaturated substrates was investigated. Experiments were carried out between 95 and 150 °C, 10 and 15 bar and without solvent. Optimal catalyst activity regarding hydrogenation of C C bonds depends on the type of the catalyst and the type of the substrate. Under proper choice of reaction conditions activities a (mmol product/mmol cat-min) of 100 to 700 could be adjusted. The C O bond is only hydrogenated by catalyst IrH3[PPh3]3 with moderate activity. 相似文献
86.
J. Becker H.G. Andresen J.R.M. Annand K. Aulenbacher K. Beuchel J. Blume–Werry Th. Dombo P. Drescher M. Ebert D. Eyl A. Frey P. Grabmayr T. Großmann P. Hartmann T. Hehl W. Heil C. Herberg J. Hoffmann J.D. Kellie F. Klein K. Livingston M. Leduc M. Meyerhoff H. Möller Ch. Nachtigall A. Natter M. Ostrick E.W. Otten R.O. Owens S. Plützer E. Reichert D. Rohe M. Schäfer H. Schmieden R. Sprengard M. Steigerwald K.-H. Steffens R. Surkau Th. Walcher R. Watson E. Wilms 《The European Physical Journal A - Hadrons and Nuclei》1999,6(3):329-344
The electric form factor of the neutron GEn has been determined in double polarized exclusive 3
He(e,e'n) scattering in quasi–elastic kinematics by measuring asymmetries A
⊥, A
∥ of the cross section with respect to helicity reversal of the electron, with the nuclear spin being oriented perpendicular
to the momentum transfer q in case of A⊥ and parallel in case of A∥. The experiment was performed at the 855 MeV c. w. microtron MAMI at Mainz. The degree of polarization of the electron beam
and of the gaseous 3
He target were each about 50%. Scattered electrons and neutrons were detected in coincidence by detector arrays covering large
solid angles. Quasi–elastic scattering events were reconstructed from the measured electron scattering angles ϑe, φe and the neutron momentum vector p
n
′ in the plane wave impulse approximation. We obtain the result <G
En>(0.27 < Q2c2/GeV2 < 0.5)= 0.0334 ± 0.0033stat± 0.0028syst which is averaged over the indicated range of Q
2, the squared momentum transfer. This G
En value is significantly smaller than measured from the D(e,e'n) reaction under similar kinematical conditions. To what extent final state interactions in 3He quench the G
En result is subject of calculations currently in progress elsewhere.
Received: 29 April 1999 相似文献
87.
Boyuan Zhang Cedric Schaack Claudia R. Prindle Ethan A. Vo Miriam Aziz Michael L. Steigerwald Timothy C. Berkelbach Colin Nuckolls Latha Venkataraman 《Chemical science》2023,14(7):1769
Electric fields have been used to control and direct chemical reactions in biochemistry and enzymatic catalysis, yet directly applying external electric fields to activate reactions in bulk solution and to characterize them ex situ remains a challenge. Here we utilize the scanning tunneling microscope-based break-junction technique to investigate the electric field driven homolytic cleavage of the radical initiator 4-(methylthio)benzoic peroxyanhydride at ambient temperatures in bulk solution, without the use of co-initiators or photochemical activators. Through time-dependent ex situ quantification by high performance liquid chromatography using a UV-vis detector, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with the solvent dielectric constant. Using density functional theory calculations, we show that the applied electric field decreases the dissociation energy of the O–O bond and stabilizes the product relative to the reactant due to their different dipole moments.We demonstrate that electric fields can homolytically cleave a peroxide bond in different solvents with a rate that is proportional to the solvent dielectric constant. 相似文献
88.
L. Jentjens K. Peithmann K. Maier H. Steigerwald T. Jungk 《Applied physics. B, Lasers and optics》2009,95(3):441-445
Irradiation of 5% magnesium-doped lithium niobate crystals (LiNbO3:Mg) with high-energy, low-mass 3He ions, which are transmitted through the crystal, changes the domain reversal properties of the material. This enables easier
domain engineering compared to non-irradiated material and assists the formation of small-sized periodically poled domains
in LiNbO3:Mg. Periodic domain structures exhibiting a width of ≈520 nm are obtained in radiation-damaged sections of the crystals.
The ferroelectric poling behavior between irradiated and non-treated material is compared. 相似文献
89.
Miao Q Chi X Xiao S Zeis R Lefenfeld M Siegrist T Steigerwald ML Nuckolls C 《Journal of the American Chemical Society》2006,128(4):1340-1345
This study explores the assembly in the crystalline state of a class of pentacenes that are substituted along their long edges with aromatic rings forming rigid, cruciform molecules. The crystals were grown from the gas phase, and their structures were compared with DFT-optimized geometries. Both crystallographic and computed structures show that a planar acene core is the exception rather than the rule. In the assembly of these molecules, the phenyl groups block the herringbone motif and further guide the arrangement of the acene core into higher order structures. The packing for the phenyl-substituted derivatives is dictated by close contacts between the C-H's of the pendant aromatic rings and the carbons at the fusions in the acene backbone. Using thiophene substituents instead of phenyls creates cofacially stacked acenes. In thin films, the thiophene-substituted derivative forms devices with good electrical properties: relatively high mobility, high ON/OFF ratios, and low threshold voltage for device activation. An unusual result is obtained for the decaphenyl pentacene when devices are fabricated on its crystalline surface. Although its acene cores are well isolated from each other, this material still exhibits good electrical properties. 相似文献
90.
Angulo J Langpap B Blume A Biet T Meyer B Krishna NR Peters H Palcic MM Peters T 《Journal of the American Chemical Society》2006,128(41):13529-13538
The biosynthesis of human blood group B antigens is accomplished by a highly specific galactosyltransferase (GTB). On the basis of NMR experiments, we propose a "molecular tweezers mechanism" that accounts for the exquisite stereoselectivity of donor substrate selection. Transferred NOE experiments for the first time reveal the bioactive conformation of the donor substrate UDP-galactose (UDP-Gal) and of its enzymatically inactive analogue, UDP-glucose (UDP-Glc). Both bind to GTB in a folded conformation that is sparsely populated in solution, whereas acceptor ligands bind in a conformation that predominates in solution. The bound conformations of UDP-Gal and UDP-Glc are identical within experimental error. Therefore, GTB must discriminate between the two activated sugars on the basis of a hitherto unknown transition state that can only be formed in the case of UDP-Gal. A full relaxation and exchange matrix analysis of STD NMR experiments reveals that acceptor substrates dissociate significantly faster (k(off) > 100 Hz) from the binding pocket than donor substrates (k(off) approximately 10 Hz). STD NMR experiments also directly show that proper recognition of the hexopyranose rings of the UDP sugars requires bivalent metal cations. At the same time, this analysis furnishes the complete three-dimensional structure of the enzyme with its bound donor substrate UDP-Gal on the basis of a prior crystal structure analysis. We propose that, upon acceptor binding, GTB uses the Asp 302 and Glu 303 side chains as "molecular tweezers" to promote bound UDP-Gal but not UDP-Glc into a transition state that leads to product formation. 相似文献