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81.
82.
Munetaka Takeuchi Yasuo Kameda Yasuhiro Umebayashi Sari Ogawa Takaaki Sonoda Shin-ichi Ishiguro Miho Fujita Mitsuru Sano 《Journal of Molecular Liquids》2009,148(2-3):99-108
Self-diffusion coefficients of Li+ DLi+, PF6− DPF6− and solvent propylene carbonate (PC) DPC in LiPF6−PC solutions were determined at 298 K by the pulse gradient spin echo (PGSE) NMR technique over the salt concentration range of 0.1–3.0 M (M = mol dm– 3). The order of the diffusion coefficients was found to be DLi+ < DPF6− < DPC over the concentration range examined, and they were monotonically decreased with increasing the salt concentration. Haven ratio Λ/ΛNMR, where Λ and ΛNMR represent the ionic conductivity measured electrochemically and that estimated via the Nernst-Einstein equation using the diffusion coefficient, respectively, was evaluated as the measure of the ion–ion interaction in the LiPF6–PC solutions. Though Λ/ΛNMR values for LiPF6-solutions decrease with increasing the salt concentration, they were greater than those for LiBF4–PC solutions over the whole concentration range examined, which indicates that the ion pair formation ability of PF6– ion is weaker than that of the BF4– ion. The smaller value of the ionic conductivity for the highly concentrated LiPF6–PC solution (above 2.0 M) than that of the LiBF4-solutions can be attributed to the more rapidly increased viscosity relative to the LiBF4-solution. Classic molecular dynamics (MD) simulations for the respective LiPF6 and LiBF4-solution of 0.5 and 1.0 M were also carried out based on the effective pair potentials. Diffusion coefficients, ionic conductivity and Haven ratio for these solutions were calculated from MD trajectories, and they qualitatively agree with those evaluated by experiments. Pair correlation functions gLiO(r) (for Li+–O (PC) pair) and gLiPF6(r) (for Li+–PF6– pair) or gLiBF4(r) (for Li+–BF4– pair) revealed that the lithium ion weakly forms the contact ion pairs with PF6–, whilst strongly with BF4–, which supports the present experimental results. Moreover, the simulation results show that both anions in the contact ion pairs predominantly take the monodentate form, which is in contrast to the multidentate coordination predicted by ab initio calculation in gas phase. 相似文献
83.
Saburo Yuasa Masaru Kawashima Takashi Sakurai 《Proceedings of the Combustion Institute》2009,32(2):1929-1936
To examine the pyrophoric characteristics of Mg powder, we generated ultra-fine Mg particles (average particle diameter: about 0.3 μm) without an original oxide coat in an Ar stream. The ignition of the powder was measured by using the impinging O2/N2 mixture streams over a wide range of the experimental parameters: pressure, oxygen concentration and velocity of the streams. The Mg powder was found to ignite even at room temperature. The spontaneous ignition temperatures in the range of 278 324 K were insensitive to all the experimental parameters. The ignition delay time had a tendency to decrease with increasing experimental parameters.The ignition process of the Mg powder was found to be controlled by the surface reaction rate without an oxide coat. We proposed a new ignition hypothesis considering a critical oxide thickness on the Mg powder particles at the transition temperature from protective to non-protective nature: that is, the ignition of the Mg powder occurs when the powder temperature rises above the transition temperature before surface reactions form a protective oxide coat with the critical thickness on the individual particle surfaces. According to this hypothesis, an ignition model of Mg powder cluster was developed, and the relation between the spontaneous critical ignition temperature and the ultra-fine powder size, depending on the critical thickness of the protective oxide coat, was clarified. The critical oxide thickness was estimated. 相似文献
84.
Miho Tanaka Kazuya Takahashi Tatsuya Urabe Tomohiro Oikawa Masao Nemoto Hideki Nagashima 《Rapid communications in mass spectrometry : RCM》2009,23(5):698-704
Silica, represented by SiO2, is the general name for the compounds composed of Si, O and H with their derivative complexes. Silica forms various chemical species in aquatic solutions, such as a monomer (Si(OH)3O−), dimer (Si2(OH)5O), and others. These species are known to vary in their relative abundances in solution depending on the chemical and physical conditions. Silica species dissolved in seawater have been examined by fast-atom bombardment mass spectrometry (FAB-MS) to elucidate the behavior of silica and its circulation as a novel tracer reflecting the chemical and physical conditions of seawater and the bioactivity of diatoms, which take up silica. In the seawater of Tokyo Bay, silica species such as [Si(OH)2O2Na]− ([monomer–Na]−), [Si2(OH)5O2]− ([dimer]−), [Si2(OH)4O3Na]− ([dimer–Na]−), [Si4(OH)7O5]− ([cyclic tetramer]−), [Si4(OH)6O6Na]− ([cyclic tetramer–Na]−), [Si4(OH)9O4]− ([linear tetramer]−) and [Si4(OH)8O5Na]− ([linear tetramer–Na]−) were observed and assigned by FAB-MS. To investigate the suitability of silica species as a tracer, the relative peak intensity ratios of silica species observed in the mass spectra, i.e. the profiles of the ratio of the linear tetramer to the cyclic tetramer (m/z 329/311) and the ratio of the dimer to the cyclic tetramer (m/z 173/311) against depth, were examined to determine the annual changes and reproducibility of the depth profiles. In particular, the depth profile of the relative ratio of the linear tetramer to the cyclic tetramer, 329/311, exhibits critical changes depending on the seawater budget. These changes in the relative ratios were identified by an experiment involving a simple sodium chloride solution system. Our measurement is expected to elucidate the dynamics of silica and its role as ‘food’ for diatoms, and we showed that speciation using mass spectrometry is a powerful tool for examining elemental behavior in nature and environmental changes. Our results suggest that a silica tracer is useful for investigating the behavior of seawater in small coastal regions and the uptake of silica by diatoms. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
85.
The fluorescence intensity of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (TPPZ) begins to increase at concentrations of metal ions (Mn+) above the 1:2 ratio of metal ion concentration to the initial concentration of TPPZ ([Mn+]/[TPPZ]0 > 0.5), when a 2:1 complex of TPPZ with Mn+ [(TPPZ)2-Mn+] is converted to a 1:1 complex of TPPZ with Mn+ (TPPZ-Mn+), which exhibits strong fluorescence. 相似文献
86.
To study the interaction between liposomes and proteins, intact liposomes were immobilized on a metal planar support by chemical binding and/or bioaffinity using a quartz crystal microbalance (QCM). A large decrease in the resonance frequency of quartz crystal was observed when the QCM, modified by a self-assembled monolayer (SAM) of carboxythiol, was added to liposome solutions. The stable chemical immobilization of intact liposomes onto SAM was judged according to the degree with which adsorbed mass depended on the prepared size of liposomes, as well as on the activation time of SAMs when amino-coupling was introduced, where the liposome coverage of electrodes was 69+/-8% in optimal conditions. When avidin-biotin binding was used on amino-coupling liposome layers, liposome immobilization finally reached 168% coverage of the electrode surface. Denatured protein was also successfully detected according to the change in the frequency of the liposome-immobilized QCM. The adsorbed mass of denatured carbonic anhydrase from bovine onto immobilized liposomes showed a characteristic peak at a concentration of guanidine hydrochloride that corresponded to a molten globule-like state of the protein, although the mass adsorbed onto deactivated SAM increased monotonously. 相似文献
87.
SK Podiyanachari R Fröhlich CG Daniliuc JL Petersen G Kehr G Erker N Suzuki S Yuasa K Hagimori S Inoue T Asada T Takemoto Y Masuyama 《Dalton transactions (Cambridge, England : 2003)》2012,41(35):10811-10816
The reaction of η(2)-iminozirconocene chloride complexes with trimethylsilylethynyl lithium leads to rapid C-C coupling at room temperature to yield the corresponding five-membered aza-zirconacycloallenoids. Such compounds were also obtained by trapping of in situ generated zirconocene with alkynyl imines. 相似文献
88.
Kuramochi Y Nakagawa T Yokoo T Yuasa J Kawai T Hasegawa Y 《Dalton transactions (Cambridge, England : 2003)》2012,41(22):6634-6640
We synthesized Eu(III) and Sm(III) complexes with tridentate phosphine oxide ligands, Eu(hfa)(3)(TPPM) and Sm(hfa)(3)(TPPM) (hfa: hexafluoroacetylacetonato, TPPM: tris(diphenylphosphinyl)methane), and we then examined their luminescent properties. In the complexes the Eu(III) and Sm(III) centres were fully surrounded by low-vibrational frequency ligands, which led to relatively high emission quantum yields (Φ(Eu) = 30%, Φ(Sm) = 4.7%). The X-ray single crystal structures of the Eu(hfa)(3)(TPPM) revealed nona-coordinated Eu(III) complexes and C-H/O hydrogen bonding formations between the acidic hydrogen atom of the TPPM ligand and oxygen atoms of solvent molecules. The C-H/O hydrogen bonding slightly affected the coordination structure around the Eu(III) ion. Despite the seemingly small effect on the structural change, because the emission band profile of the (5)D(0)→(7)F(2) transition is sensitive to changes in the coordination environment of the Eu(III) complex, we observed a red shift in the emission spectral line. 相似文献
89.
H Kobayashi H Morita M Yamauchi R Ikeda H Kitagawa Y Kubota K Kato M Takata S Toh S Matsumura 《Journal of the American Chemical Society》2012,134(30):12390-12393
We have synthesized and characterized homogeneous solid-solution alloy nanoparticles of Pd and Rh, which are immiscible with each other in the equilibrium bulk state at around room temperature. The Pd-Rh alloy nanoparticles can absorb hydrogen at ambient pressure and the hydrogen pressure of Pd-Rh alloys for hydrogen storage is dramatically decreased by more than 4 orders of magnitude from the corresponding pressure in the metastable bulk state. The solid-solution state is still maintained in the nanoparticles even after hydrogen absorption/desorption, in contrast to the metastable bulks which are separated into Pd and Rh during the process. 相似文献
90.
We report nanosize-induced hydrogen storage in Ir, which does not absorb hydrogen in its bulk form. The mean diameter of the obtained Ir nanoparticles was estimated as 1.5 ± 0.5 nm by transmission electron microscopy. Hydrogen storage was confirmed by solid-state (2)H NMR and hydrogen pressure-composition isotherm measurements. 相似文献