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61.
Photoelectron spectra from metallic systems always show asymmetric core lines. One effect of this asymmetry is to shift the peak position of a core level spectrum away from the ground state energy of the core hole state. In this letter, M and N core level binding energies for the 5th period elements are reported which have been corrected for the effect of the asymmetry. In some cases the relative energy positions have been compared to accurate X-ray data. The results indicate that even when fairly broad core electron lines are involved, accurate core level separations can be determined. 相似文献
62.
Neutral cyclodextrins as chiral agents for enantiomeric separations of chromanes in capillary electrophoresis 总被引:1,自引:0,他引:1
A. Fridström L. Nyholm Th. Netscher W. Walther N. Lundell K. E. Markides 《Chromatographia》1997,44(5-6):313-319
Summary Six different cyclodextrins with varying cavity size and rim substitution were used as chiral agents for the enantiomeric
separation of eight chromane compounds or analogues using capillary electrophoresis. It is shown that the cyclodextrin type
and concentration have a large influence on the enantiomeric separation obtained for these compounds. A chiral resolution
of 1.4 or better could be obtained for all the substances with either substituted heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin
or unsubstituted γ-cyclodextrin as the chiral selector. The influence of the γ-cyclodextrin concentration, ionic strength
and pH on the chiral separations was also investigated with a multivariate screening design. The detection limit and resolution
of the present method allow determinations of the investigated compounds down to a chiral impurity of less than 0.1 % (area/area). 相似文献
63.
64.
Deviceless decoupled electrochemical detection of catecholamines in capillary electrophoresis using gold microband array electrodes 总被引:2,自引:0,他引:2
Samples containing microM concentrations of dopamine, (+/-)-isoproterenol, para-aminophenol and chlorogenic acid have been separated by capillary electrophoresis (CE) and detected using end-column amperometric detection based on a novel decoupling method. The present decoupling approach involves the use of an electrochemical detector chip containing an array of microband electrodes where the working and reference electrodes are positioned only 10 microm from each other. The short distance between the working and reference electrodes ensures that both electrodes are very similarly affected by the presence of the CE electric field. With this method, no shift in the detection potential was seen when the CE high voltage was applied. This eliminated the need for a reoptimization of the detection potential to compensate for the influence of the separation voltage on the detection. It is also demonstrated that catecholamines can be detected using gold microband electrodes by careful adjustment of the detection potential to avoid the formation of gold oxide. Such careful adjustments of the detection potential are straightforward using the present decoupling method. 相似文献
65.
66.
Eilers G Zettersten C Nyholm L Hammarström L Lomoth R 《Dalton transactions (Cambridge, England : 2003)》2005,(6):1033-1041
The structural rearrangements triggered by oxidation of the dinuclear Mn complex [Mn(2)(bpmp)(mu-OAc)2]+(bpmp = 2,6-bis[bis(2-pyridylmethyl)amino]methyl-4-methylphenol anion) in the presence of water have been studied by combinations of electrochemistry with IR spectroscopy and with electrospray ionization mass spectrometry (ESI-MS). The exchange of acetate bridges for water (D2O) derived ligands in different oxidation states could be monitored by mid-IR spectroscopy in CD(3)CN-D(2)O mixtures following the v(as(C-O)) bands of bound acetate at 1594.4 cm(-1)(II,II), 1592.0 cm(-1)(II,III) and 1586.5 cm(-1)(III,III). Substantial loss of bound acetate occurs at much lower water content (< 0.5% v/v) in the III,III state than in the II,II and II,III states (> or = 10%). The ligand-exchange reactions do not initially reduce the overall charge of the complex but facilitate further oxidation by proton-coupled electron transfer as the water-derived ligands are increasingly deprotonated in higher oxidation states. In the IR spectra deprotonation could be followed by the formation of acetic acid (DOAc, approximately 1725 cm(-1), v(C-O)) from the released acetate (1573.6 cm(-1), v(as(C-O))). By the on-line combination of an electrochemical flow cell with ESI-MS several product complexes could be identified. A di-mu-oxo bridged III,IV dimer [Mn(2)(bpmp)(mu-O)(2)](2+)(m/z 335.8) can be generated at potentials below the III,III/II,III couple of the di-mu-acetato complex (0.61 V vs. ferrocene). The ligand-exchange reactions allow for three metal-centered oxidation steps to occur from II,II to III,IV in a potential range of only 0.5 V, explaining the formation of a spin-coupled III,IV dimer by photo-oxidation with [Ru[bpy)(3)](3+) in previous EPR studies. 相似文献
67.
Experimental photoelectron spectra of a clean polycrystalline Mo surface excited by monochromatized Al K α X-rays are presented. The spectra are compared with valence bands obtained by UPS and by band structure calculations within the 5 eV region below the Mo Fermi level. All results mentioned above display peaks at 0.3, 1.7, 2.8 and 4 eV belowE F. The energy distribution of the valence band does not vary with photon energy and electron emission angle for the four different polycrystalline Mo surfaces compared. It is concluded that the four peaks representing the Mo valence band are predominantly of bulk origin. 相似文献
68.
The atmospheric pressure ionization process obtained when a mixture of methanol and water (90:10, v/v) also containing 50 microM sodium hydroxide is dispersed from a fused-silica emitter was studied. A combination of a high electric field and a nebulizer gas with the high voltage applied upstream in the liquid flow was utilized to facilitate the spray process. By comparing the dependences of the spray current and ion signals on the spray potential, it was found that electrical corona discharges were obtained for potentials higher than about 2.6 kV, which resulted in a mixed electrospray and chemical ionization process. By introducing vapour from a solvent, such as benzene or toluene, with a low ionization energy into the nebulizing gas, it was found that the appearance of the corresponding molecular ion was correlated with a change in the slope of the spray current-potential curve. This indicates that the breakpoints in the spray current-potential curves observed were correlated with the onsets of corona discharges. It was shown that the mixed ionization process gives rise to increased amounts of protonated solvent molecules and assists in the formation of sodiated adduct ions from an uncharged fatty acid methyl ester. 相似文献
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70.