992 resultados para ELECTRON-SPIN POLARIZATION
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The x-ray and gamma-ray induced damage in BaLiF3 crystallites and its suppression by rare earth ion doping have been studied by electron spin resonance and thermally stimulated luminescence methods. It has been found that the x-ray irradiation damage is light and can be erased easily. This shows that the BaLiF3 crystallite is an ideal host for x-ray storage material. But the damage induced by gamma-ray has been found to be relatively hard to recover; however the gamma-ray irradiation hardness can be improved by rare earth (e.g., La3+, Yb3+) ion doping. So the BaLiF3 is also promising material for being used in detection of high-energy particles (e.g., gamma-ray).
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The rare earth complex oxides with different types have been synthesized. Their structures and electric properties have been investigated. According to our experimental results, the effects of the outest shell electronic configuration, electron spin state, electron transport path and formation of cluster on the electric properties of rare earth complex oxides have been summarized. When the electrons in the outest shell of the central metallic ion are unpair, and the outest shell is not half-filled, the electric conductibilities of these compounds are better, If there is a -M-X-M-X- or -M-M-M- (the distances between two atoms <0.31 nm) continuous electron transport path, and the electron configurations of the central metallic ion conform to the above condition, then the electric conductibilities are good, The isolate cluster can not become the continuous electron transport path, therefore, the formation of the isolate cluster will reduce the conductibility.
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The electrochemical reduction behavior of bilirubin (BR) at platinum electrode in DMF was investigated by cyclic voltammetry, in situ electron spin resonance spectroscopy and in situ rapid scanning thin layer spectroelectrochemistry. Experimental results revealed that the reduction of BR firstly undergoes an ECE process: GRAPHICS The generated (BR)(2)(3-). can be re-oxidized to BR and then to purpurin (Pu) by a series of oxidation processes: GRAPHICS However, the re-reduction reactions of Pu are not the reverse processes. The different reduction mechanisms are discussed in detail.
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In this paper, the graft copolymers of styrene to nascent linear polyethylene reactor powders were prepared through plasma graft polymerization. The grafting reaction was initiated by the alkyl radicals formed on the surface of nascent polyethylene with plasma treatment as indicated by electron spin resonance spectra. In graft copolymerization by alkyl radicals, the grafting yield increased with either the plasma power or the plasma treatment lime. Compared with ordinary polyethylene powders, nascent polyethylene reactor powders were found to be more easily plasma-grafted. This has been attributed to the greater sensitivity to irradiation in producing reactive centres under the same conditions. High density polyethylene showed almost the same grafting yield as linear low density polyethylene at 50 degrees C. The surface morphology of nascent polyethylene observed by scanning electron microscope before and after the grafting showed that the silk-like fibrils were not destroyed by plasma treatment.
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ESR method has been used to study superhyperfine. interaction of I-127 in [Cu (IO5OH)(2)](5-) ion for Na4KCu(IO5OH)(2) . 12H(2)O single crystal. The main purpose of this paper is to confirm the existence of unpaired electron spin on iodine atom and to find a reasonable explanation for the spin delocalization of CU2+ ions. Based on the ESR parameters of paramagnetic [Cu(IO5OH)(2)](5-) ions, the calculated results show that about 0.77% of the unpaired eletron spin is located on each iodine atom.
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Radiation effects on polyamide-1010 specimens having various states of aggregation were studied using wide angle X-ray diffraction, electron spin resonance, calorific and sol measurement techniques. Experimental results indicated that chain crosslinking
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The electrooxidation behavior of bilirubin (BR), biliverdin (BV), purpurin (Pu), and choletelin (Ch in dimethylformamide (DMF) have been investigated bv voltammetry, in situ electron spin resonance (ESR) thin-layer spectroelectrochemistry and especially i
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Polyvinyl alcohol amidoxime (PVAAO) chelate fiber prepared in our laboratory is a good adsorbent. Comparing with other adsorbents, it has many advantages, such as higher hydrophilicity, better adsorbability and easier synthesis. In this work, the synthesi
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1:12 phosphomolybdic anion doped polypyrrole film electrode was characterized by in-situ UV-vis spectroelectrochemistry, X-ray photoelectron spectroscopy(XPS), scan electronic microscopy(SEM) and electron spin resonance(ESR) spectroscopy.
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The effect of thermal treatment on H-MCM-22 and H-ZSM-5 zeolites was investigated using the electron spin resonance technique. A six-line signal (denoted as A, g = 2.048, A = 22. 15 G) was detected on H-MCM-22 after He purging at high temperatures, whose intensities increased with the treating temperature. The same signal was also found on H-ZSM-5 zeolites with different crystal sizes. The paramagnetic center was identified as a V center, namely, a hole of an electron trapped on an oxygen atom bonding to a nearby aluminum atom. These signals appeared only on a dealuminated sample or a sample concomitantly with dealumination. The formation of the hole might involve an electron transferring from the lattice oxygen to a nonframework aluminum species, and the hyperfine splitting is caused by the interaction between the electron hole locating on the p orbit of oxygen and the framework aluminum bonding with the oxygen. The signal disappeared after the sample was exposed to air or oxygen at room temperature. However, the process was reversible. A new set of signals (denoted as B, g(1) = 2.008, g(2) = 2.003, g(3) = 1.9985) was observed after oxygen adsorption on the H-MCM-22 pretreated with He at 973 K or He purging at 973 K on the H-MCM-22 pretreated with oxygen at 813 K, which was attributed to the O- species.
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Manganese-modified mesoporous MCM-41 molecular sieves were synthesized at the absence of alkaline metal ions under mild alkaline condition using cetylpyridinium bromide surfactant as a template, and characterized with X-ray diffraction, N-2 adsorption, transmission electron microscopy, electron spin resonance (ESR), and nuclear magnetic resonance (NMR) spectroscopies. The synthesized MnMCM-41 has a high pore volume of 1.30 cm(3) g(-1) with a corresponding surface area of 1510 m(2) g(-1). The ESR and Si-29 MAS NMR spectra revealed the presence of framework manganese ions in either the as-synthesized or calcined forms. (C) 2002 Elsevier Science B.V. All rights reserved.
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Silicalite-I, ZSM-5, and Fe-ZSM-5 zeolites prepared from two different silicon sources are characterized by UV resonance Raman (UVRR) spectroscopy, X-ray diffraction (XRD), electron spin resonance (ESR), and UV/visible diffuse reflectance spectroscopy (UV/Vis DRS). A new technique for investigating zeolitic structure, UV resonance Raman spectroscopy selectively enhances the Raman bands associated with framework iron atoms incorporated into MFI-type zeolites, and it is very sensitive in identifying the iron atoms in the framework of zeolites, while other techniques such as XRD, ESR, and UV/Vis DRS have failed in uncovering trace amounts of iron atoms in the framework of zeolites. (C) 2000 Academic Press.
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The chemical interplay of nitrogen oxides (NO's) with hemoglobin (Hb) has attracted considerable recent attention because of its potential significance in the mechanism of NO-related vasoactivity regulated by Hb. An important theme of this interplay-redox coupling in adducts of heme iron and NO's-has sparked renewed interest in fundamental studies of FeNO(x) coordination complexes. In this Article, we report combined UV-vis and comprehensive electron paramagnetic resonance (EPR) spectroscopic studies that address intriguing questions raised in recent studies of the structure and affinity of the nitrite ligand in complexes with Fe(III) in methemoglobin (metHb). EPR spectra of metHb/NO(2)(-) are found to exhibit a characteristic doubling in their sharper spectral features. Comparative EPR measurements at X- and S-band frequencies, and in D(2)O versus H(2)O, argue against the assignment of this splitting as hyperfine structure. Correlated changes in the EPR spectra with pH enable complete assignment of the spectrum as deriving from the overlap of two low-spin species with g values of 3.018, 2.122, 1.45 and 2.870, 2.304, 1.45 (values for samples at 20 K and pH 7.4 in phosphate-buffered saline). These g values are typical of g values found for other heme proteins with N-coordinated ligands in the binding pocket and are thus suggestive of N-nitro versus O-nitrito coordination. The positions and shapes of the spectral lines vary only slightly with temperature until motional averaging ensues at approximately 150 K. The pattern of motional averaging in the variable-temperature EPR spectra and EPR studies of Fe(III)NO(2)(-)/Fe(II)NO hybrids suggest that one of two species is present in both of the alpha and beta subunits, while the other is exclusive to the beta subunit. Our results also reconfirm that the affinity of nitrite for metHb is of millimolar magnitude, thereby making a direct role for nitrite in physiological hypoxic vasodilation difficult to justify.
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The effects of such solutes such as halides and water on the physical properties of room temperature ionic liquids (RTILs) have been extensively studied, This work examines the effect of the solute carbon dioxide on the RTIL 1-ethyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C(2)mim][NTf2]) and its influence on the electrochemical characterization of the important redox couple ferrocene/ferrocenium (Fc/Fc(+)). The system was studied using cyclic voltammetry, chronoamperometry, and electron spin resonance (ESR) spectroscopy. Addition Of 100% CO2 to a solution of Fc in [C(2)mim][NTf2] resulted in a substantial increase in both the limiting oxidative current and diffusion coefficient of Fc. Arrhenius plots of Fc diffusion coefficients in the pure and CO2-saturated ionic liquid revealed a decrease in activation energy of translational diffusion from 29.0 (+/- 0.5) kJ mol(-1) to 14.7 (+/- 1.6) kJ mol(-1), suggesting a reduction in the viscosity of the ionic liquid with addition Of CO2. ESR spectroscopy was then used to calculate the rotational correlation coefficients of a probe molecule, 2,2,6,6-tetramethyl-1-piperinyloxyl (TEMPO), to add supporting evidence to this hypothesis. Arrhenius plots of rotational correlation coefficients in the pure and CO2-saturated ionic liquid resulted in a similar drop in activation energy from 28.7 (+/- 2.1) kJ mol(-1) to 18.2 (+/- 5.6) kJ mol(-1). The effect of this solute on the ionic liquid [C(2)mim][NTf2] and on the electrochemical measurements of the Fc/Fc(+) couple emphasizes the necessity of fastidious sample preparation, as it is clear that the voltammetric currents of the electroactive species under study are influenced by the presence of CO2 in solution. The voltammetric response of the electroactive species in RTILs cannot be assumed to be independent of other solutes.
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The physical effect of high concentrations of reversibly dissolved SO2 on [C(2)mim][NTf2] was examined using cyclic voltammetry, chronoamperometry, and ESR spectroscopy. Cyclic voltammetry of the oxidation of solutions of ferrocene, N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), and chloride in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethanesufonyl)imide ([C(2)mim][NTf2]) reveals an increase in limiting current of each species corresponding to the addition of increasing concentrations of sulfur dioxide. Quantitative chronoamperometry reveals an increase in each species' diffusion coefficient with SO2 concentration. When chronoamperometric data were obtained for ferrocene in [C(2)mim][NTf2] at a range of temperatures, the translational diffusion activation energy (29.0 +/- 0.5 kJ mol(-1)) was found to be in good agreement with previous studies. Adding SO2 results in apparent near-activationless translational diffusion. A significant decrease in the activation energy of rotational diffusion with the SO2 saturation of a 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) solution in [C(2)mim][NTf2] (29.9 +/- 2.0 to 7.7 +/- 5.3 kJ mol(-1)) was observed using electron spin resonance (ESR) spectroscopy. The reversible physical absorption Of SO2 by [C(2)mim][NTf2] should have no adverse effect on the ability of that ionic liquid to be employed as a solvent in an electrochemical gas sensor, and it is possible that the SO2-mediated reduction of RTIL viscosity could have intrinsic utility.