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61.
Antoine Aboukais Elena A. Zhilinskaya Jean-Franois Lamonier Igor N. Filimonov 《Colloids and surfaces. A, Physicochemical and engineering aspects》2005,260(1-3):199-207
Oxygen adsorption experiments were performed on evacuated and prereduced CeO2/SiO2 and CeO2/Al2O3 catalysts with and without platinum. Considerable amounts of the superoxide radical ions were stabilized on all the samples. Signal parameters suggest Ce4+–O2− positioning for all detectable superoxide species. Physisorbed oxygen broadens O2− signal beyond detection for all the alumina-based samples, while the same procedure for all the silica-based samples did not change signal shape of O2− species. Detectable O2− species are localized in the bulk of ceria and the nature of support (silica or alumina) determines the number of oxygen vacancies and the rate of electron transfer. XRD data suggest that for alumina-based samples small and/or thin islands of ceria dominate, while comparatively large ceria particles are stabilized on the surface of silica-based samples with the same ceria content. Average size of ceria crystallites is still not determining factor and cannot account for the observed differences. Higher concentrations of paramagnetic species may be stabilized on alumina-based samples and thus, sensor-like behavior towards gaseous oxygen at room temperature was detected for them—oxygen admission reversibly changes superoxide lineshape. For silica samples, only minor changes of O2− lineshapes were typical upon the change of the partial pressure of oxygen at ambient and low temperatures. Addition of platinum has little effect on parameters of the O2− signal, except an enhancement of the superoxide decay in the reducing media. Possible site for O2− stabilization inside the lattice of CeO2 was proposed and relevance of the observed effects to the redox catalysis discussed. 相似文献
62.
Zheng-Huan Lin Hong-Yan Dou Jin Li Cheng-Xue Zhao 《Research on Chemical Intermediates》2005,31(9):867-873
The H-abstractions/spin-trapping reactions with primary, secondary and tertiary alcohols of new 'magic blue' reagents, namely,
the blue F113 (CClF2CCl2F) solution containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl} nitroxide (2) and perfluoro[1-nitroso-1-(2-fluorosulfonyl)ethoxy]ethane (3) both generated in the reaction of perfluoro[2-(2-fluorosulfonyl)ethoxy]propionyl peroxide (1) with sodium nitrite in F113 at room temperature, were studied by EPR. Based on the interpretation of the EPR spectra of
the spin adducts, nitroxides, the region-selectivity of H-abstraction has been disclosed and the possible mechanistic paths
of H-abstraction have also been discussed. EPR of H-abstraction by using 'magic blue' reagents can also be used for producing
various hydroxyalkyl radicals from common alcohols. 相似文献
63.
B. G. Ershov A. F. Seliverstov N. L. Sukhov G. L. Bykov 《Russian Chemical Bulletin》1992,41(10):1805-1809
The sorption of Cu2+ ions by chitin and chitosan from aqueous solutions has been investigated, as well as the molecular structure of the complexes formed. The static exchange capacities have been determined, equal to 3.5 and 0.25 mmole/g for chitosan and chitin, respectively, and the partition coefficients (5000 and 70 g/ml). It has been shown that in complex formation a bond with the amino group is formed as the result of the substitution of a proton in the latter. The EPR spectra of these complexes have been obtained and their radiospectroscopic parameters determined (g
= 2.334,g
= 2.054,A = 0.0156 cm–1, andB = 0.0028 cm–1 for chitin, andg
= 2.231,g
= 2.048,A = 0.0192 cm–1, andB = 0.0025 cm–1 for chitosan). For chitosan the ligands are two nitrogen atoms of the amino groups and two oxygen atoms of the hydroxyl groups in the position C3 of adjacent glucosamine rings; for chitin, the oxygen atoms of the acetyl groups take part in addition in the complex formation. The analysis of the radiospectroscopic parameters and their comparison with published data lead to the conclusion that the Cu2+ complex with chitosan has a tetragonal symmetry, while the complex with chitin most probably has an octahedral structure.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2305–2311, October, 1992. 相似文献
64.
The electron paramagnetic resonance (EPR) spectra of gamma irradiated single crystals of alpha-benzoinoxime (ABO) have been examined between 120 and 440 K. Considering the dependence on temperature and the orientation of the spectra of single crystals in the magnetic field, we identified two different radicals formed in irradiated ABO single crystals. To theoretically determine the types of radicals, the most stable structure of ABO was obtained by molecular mechanic and B3LYP/6-31G(d,p) calculations. Four possible radicals were modeled and EPR parameters were calculated for the modeled radicals using the B3LYP method and the TZVP basis set. Calculated values of two modeled radicals were in strong agreement with experimental EPR parameters determined from the spectra. Additional simulated spectra of the modeled radicals, where calculated hyperfine coupling constants were used as starting points for simulations, were well matched with experimental spectra. 相似文献
65.
Large Zero‐Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles 下载免费PDF全文
Samantha A. Magee Dr. Stephen Sproules Dr. Anne‐Laure Barra Dr. Grigore A. Timco Nicholas F. Chilton Prof. David Collison Prof. Richard E. P. Winpenny Prof. Eric J. L. McInnes 《Angewandte Chemie (International ed. in English)》2014,53(21):5310-5313
[Ru2Mn(O)(O2CtBu)6(py)3] has an S=5/2 ground state with a very large zero‐field splitting (ZFS) of D=2.9 cm?1, as characterized by EPR spectroscopy at 4–330 GHz. This is far too large to be due to the MnII ion (D <0.2 cm?1), as shown from the {Fe2Mn} analogue, but can be modeled by antisymmetric exchange effects. 相似文献
66.
B. A. Salakhutdinov D. N. Dalimov T. F. Aripov I. I. Tukfatullina R. Kh. Ziyatdinova A. Zh. Dzhuraev F. G. Kamaev L. Yu. Izotova B. T. Ibragimov I. Mavridis P. Giastas 《Chemistry of Natural Compounds》2002,38(3):249-256
Derivatives of 3-O-acetyl-18-H-glycyrrhetic acid were synthesized. Their structures and membrane activities were studied. 相似文献
67.
Dr. Kyohei Otsuka Naozumi Matsumoto Dr. Shintaro Ishida Prof. Dr. Soichiro Kyushin 《Angewandte Chemie (International ed. in English)》2015,54(27):7833-7836
The radical anion of octa‐tert‐butyloctasilacubane was generated and isolated. The EPR spectrum showed the satellites due to the tertiary 13C nuclei of the eight tert‐butyl groups. The X‐ray crystallographic analysis showed that the Si? Si bonds are shortened and the Si? C bonds are elongated compared with those of octa‐tert‐butyloctasilacubane. These results are well explained by the distribution of an unpaired electron in the singly occupied molecular orbital (SOMO). 相似文献
68.
69.
Curto CA Placidi G Sotgiu A Alecci M 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):353-358
We present an open volume, high isolation, RF system suitable for pulsed NMR and EPR spectrometers with reduced dead time. It comprises a set of three RF surface coils disposed with mutually parallel RF fields and a double-channel receiver (RX). Theoretical and experimental results obtained with a prototype operating at about 100 MHz are reported. Each surface RF coil (diameter 5.5 cm) was tuned to f0 = 100.00 ± 0.01 MHz when isolated. Because of the mutual coupling and the geometry of the RF coils, only two resonances at f1 = 97.94 MHz and f2 = 101.85 MHz were observed. We show they are associated with two different RF field spatial distributions. In continuous mode (CW) operation the isolation between the TX coil and one of the RX coils (single-channel) was about −10 dB. By setting the double-channel RF assembly in subtraction mode the isolation values at f1 or f2 could be optimised to about −75 dB. Following a TX RF pulse (5 μs duration) an exponential decay with time constant of about 600 ns was observed. The isolation with single-channel RX coil was about −11 dB and it increased to about −47 dB with the double-channel RX in subtraction mode. Similar results were obtained with the RF pulse frequency selected to f2 and also with shorter (500 ns) RF pulses. The above geometrical parameters and operating frequency of the RF assembly were selected as a model for potential applications in solid state NMR and in free radical EPR spectroscopy and imaging. 相似文献
70.
Optimization of magnetic field sweep and field modulation amplitude for continuous-wave EPR oximetry
Palmer J Potter LC Ahmad R 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,209(2):337-340
For continuous-wave electron paramagnetic resonance spectroscopy, what settings of magnetic field sweep width and field modulation amplitude yield the best accuracy in estimated linewidth? Statistical bounds on estimation error presented in this work provide practical guidance: set the sweep width and modulation amplitude to 8 and 4 times the half-width half-maximum linewidth, Γ, respectively. For unknown linewidths in the range [Γ(min),Γ(max)] the worst-case estimation error is minimized by using settings designed for Γ(max). The analysis assumes a Lorentzian lineshape and a constant modulation amplitude across the extent of the irradiated paramagnetic probe. The analytical guidelines are validated using L-band spectroscopy with a particulate LiNc-BuO probe. 相似文献