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Gonnade RG Iwama S Sugiwake R Manoj K Takahashi H Tsue H Tamura R 《Chemical communications (Cambridge, England)》2012,48(22):2791-2793
Nearly racemic ketoprofen, which satisfies the requirements for the occurrence of preferential enrichment, was spontaneously resolved into the two enantiomers by simple crystallization under nonequilibrium conditions using high concentrations. 相似文献
53.
Futamura R Iiyama T Hamasaki A Ozeki S 《Physical chemistry chemical physics : PCCP》2012,14(2):981-986
The density and intermolecular structure of water in carbon micropores (w = 1.36 nm) are investigated by small-angle X-ray scattering (SAXS) and X-ray diffraction (XRD) measurements between 20 K and 298 K. The SAXS results suggest that the density of the water in the micropores increased with increasing temperature over a wide temperature range (20-277 K). The density changed by 10%, which is comparable to the density change of 7% between bulk ice (I(c)) at 20 K and water at 277 K. The results of XRD at low temperatures (less than 200 K) show that the water forms the cubic ice (I(c)) structure, although its peak shape and radial distribution functions changed continuously to those of a liquid-like structure with increasing temperature. The SAXS and XRD results both showed that the water in the hydrophobic nanospaces had no phase transition point. The continuous structural change from ice I(c) to liquid with increasing temperature suggests that water shows negative thermal expansion over a wide temperature range in hydrophobic nanospaces. The combination of XRD and SAXS measurements makes it possible to describe confined systems in nanospaces with intermolecular structure and density of adsorbed molecular assemblies. 相似文献
54.
Hanping He Dr. Masaki Hagihara Dr. Kazuhiko Nakatani Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(40):10641-10648
A newly designed ligand, methylcarbamoylnaphthyridine dimer (MCND), was synthesized and characterized. Ligand binding to d(GAA)10 was investigated by UV thermal denaturation, circular dichroism spectroscopy, surface plasmon resonance, and cold‐spray‐ionization time‐of‐flight mass spectrometry. The results indicated that MCND bound to the d(GAA)n repeat to form a stable hairpin structure with a major binding stoichiometry of 3:1. The most likely binding site was identified as the G? G mismatch in the AGA/AGA triad. The polymerase stop assay showed that MCND binding to the d(GAA)n repeat effectively interfered with the extension of the primer at the first two GAA sites on the template with both prokaryotic Taq DNA polymerase and human DNA polymerase α. 相似文献
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Mechanism of radiation hardening by single halogen interstitials has been studied in KBr. It is found that the interstitial ions more strongly interrupt dislocation movements than the atoms do. The IA center-dislocation interaction involves thermal activation. The maximum force in the interaction process is obtained to be 1.6 x 10-4 dyne. The results of linear elastic calculations suggest that this interaction is elastic in nature. 相似文献
58.
Kishimoto N Hagihara Y Ohno K Knippenberg S François JP Deleuze MS 《The journal of physical chemistry. A》2005,109(46):10535-10546
We report on the results of an exhaustive study of the interplay between the valence electronic structure, the topology and reactivity of orbitals, and the molecular structure of biphenyl by means of Penning ionization electron spectroscopy in the gas phase upon collision with metastable He*(2(3)S) atoms. The measurements are compared with one-particle Green's function calculations of one-electron and shake-up valence ionization spectra employing the third-order algebraic diagrammatic construction scheme [ADC(3)]. Penning ionization intensities are also analyzed by means of the exterior electron-density model and comparison with photoelectron spectra: in contrast with the lines originating from sigma orbitals, ionization lines belonging to the pi-band system have large Penning ionization cross sections due to their greater extent outside the molecular van der Waals surface. The involved chemi-ionization processes are further experimentally investigated using collision-energy-resolved Penning ionization electron spectroscopy. The cross sections of pi-ionization bands exhibit a markedly negative collision-energy dependence and indicate that the interaction potential that prevails between the molecule and the He*(2(3)S) atom is strongly attractive in the pi-orbital region. On the other hand, the partial ionization cross sections pertaining to sigma-ionization channels are characterized by more limited collision-energy dependencies, as a consequence of rather repulsive interactions within the sigma-orbital region. A comparison of ADC(3) simulations with the Penning ionization electron spectra and UV photoelectron spectra measured by Kubota et al. [Chem. Phys. Lett. 1980, 74, 409] on thin films of biphenyl deposited at 170 and 109 K on copper demonstrates that biphenyl molecules lying at the surface of polycrystalline layers adopt predominantly a planar configuration, whereas within an amorphous sample most molecules have twisted structures similar to those prevailing in the gas phase. 相似文献
59.
Sato S Fukuda M Hagihara M Tanabe Y Ohkubo K Morii T 《Journal of the American Chemical Society》2005,127(1):30-31
The structural characteristics of RNA-peptide (RNP) complexes are suitable for molding of a ligand-binding pocket of the RNP complex in a stepwise manner. The first step involves molding of the RNA subunit by in vitro selection of an RNP pool originating from an RNA library and the peptide, as previously reported for the construction of an ATP-binding RNP complex from an RRE RNA-Rev peptide complex. The second step involves selection from an RNP library consisting of Rev peptides with randomized amino acid residues and the RNA subunit selected in the first molding. The ATP-binding pocket produced by sequential molding of RNA and peptide subunits shows higher affinity to ATP and a distinct specificity for ATP versus dATP as compared to the ATP-binding RNP receptor in which only the RNA subunit has been molded. The second step selection from the peptide-based RNP library allows expansion of the ATP recognition surface, consisting of both RNA and peptide subunits, to enhance the affinity and selectivity to discriminate ATP against dATP. Our approach of stepwise molding offers the advantage of increasing the diversity of the RNP library by utilizing characteristics of different biopolymers. The ribonucleopeptide-based, multi-subunit approach is also extendable to other biomacromolecular assemblies, which may yield artificial receptors and enzymes with increased specificity and more diverse chemical activities. 相似文献
60.
S. Takahashi E. Murata K. Sonogashira N. Hagihara 《Journal of polymer science. Part A, Polymer chemistry》1980,18(2):661-669
The metal-polyyne polymers consisting of transition metals and conjugated tetrayne systems where M represents ? Pt(PBu3)2? or ? Pd(PBu3)2? moiety were prepared by the oxidative coupling method and characterized by spectral analysis, associated with novel depolymerization giving binuclear transition metal complexes, and 相似文献