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Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co+2FeII) and ferricyanides (Co+2FeIII) in an ozone flow. The CN stretching bands occur at 2085 cm–1 for Co+2FeII and at 2160 cm–1 for Co+2FeIII. After the ozonization process of Co+2FeII, an intense band approximately at 2125 cm–1 is detected. This intermediate band must correspond to a mixed valence state of the type: FeII–CN–Co2+–NC–FeIII Mössbauer spectra recorded in situ during the ozonization of Co+2FeII show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co+2FeII after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable. 相似文献
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Meyers CY Chan-Yu-King R Hua DH Kolb VM Matthews WS Parady TE Horii T Sandrock PB Hou Y Xie S 《The Journal of organic chemistry》2003,68(2):500-511
Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes. 相似文献
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R. G?tz P. Enge P. Friesel K. Roch B. Schilling B. Hartmann H. Wunsch 《Fresenius' Journal of Analytical Chemistry》1994,348(10):694-695
Sampling and determination of dissolved and particlebound PCBs and HCB in the river Elbe are described. A new filtration/adsorption unit for sampling of dissolved lipophilic contaminants was developed. The detection limit for dissolved PCBs and HCB was 5 pg/l. The data show that more than 98% of the PCBs and of HCB in the water of the river Elbe are particle-bound. 相似文献
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van den Brand JF Ent R Anthony PL Arnold RG Arrington J Beise EJ Belz JE Bosted PE Bulten H Chapman MS Coulter KP Dietrich FS Epstein M Filippone BW Gao H Gearhart RA Geesaman DF Hansen J Holt RJ Jackson HE Jones CE Keppel CE Kinney ER Kuhn S Lee K Lorenzon W Lung A Makins NC Margaziotis DJ McKeown RD Milner RG Mueller B Napolitano J Nelson J O'Neill TG Papavassiliou V Petratos GG Potterveld DH Rock SE Spengos M Szalata ZM Tao LH van Bibber K Wasson DA White JL Zeidman B 《Physical review D: Particles and fields》1995,52(9):4868-4871
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Makins NC Ent R Chapman MS Hansen J Lee K Milner RG Nelson J Arnold RG Bosted PE Keppel CE Lung A Rock SE Spengos M Szalata ZM Tao LH White JL Coulter KP Geesaman DF Holt RJ Jackson HE Papavassiliou V Potterveld DH Zeidman B Arrington J Beise EJ Belz E Filippone BW Gao H Lorenzon W Mueller B McKeown RD O'Neill TG Epstein M Margaziotis DJ Napolitano J Kinney E Anthony PL van Bibber K Dietrich FS Gearhart RA Patratos GG Kuhn SE van den Brand JF Bulten H Jones CE 《Physical review letters》1994,72(13):1986-1989
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Automatic classification of two-dimensional gel electrophoresis pictures by heuristic clustering analysis: a step toward machine learning 总被引:3,自引:0,他引:3
The interpretation of two-dimensional gel electrophoresis (2-DGE) profiles can be facilitated by artificial intelligence and machine learning programs. We have incorporated into our 2-DGE computer analysis system (termed MELANIE-Medical Electrophoresis Analysis Interactive Expert system) a program which automatically classifies 2-DGE patterns using heuristic clustering analysis. This program is a step toward machine learning. In this publication, we describe the classification method and the preliminary results obtained with liver biopsy electrophoretograms. Heuristic clustering is also compared to other classification techniques. 相似文献