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Intermolecular complexes between sulfide radical cations from β-hydroxy sulfides and phosphate

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image of Research on Chemical Intermediates

Triplet-sensitized oxidation of 2-(methylthio)ethanol (2-MTE) and photosensitized formaldehyde formation from 2-MTE were measured in aqueous solutions. The formaldehyde quantum yields were measured in steady-state experiments; whereas the time-resolved detection of dimeric sulfur radical cations (S∴S)+ was followed in nanosecond laser flash photolysis. 4-Carboxybenzophenone was the triplet sensitizer in both types of experiments. It was found that the lifetimes of the (S∴S)+ radicals increased in the presence of phosphate buffer, sodium perchlorate, or D2O. There were corresponding decreases in the formaldehyde yields for these same experimental factors. The phosphate case was discussed in some detail in terms of a new intermolecular complex between the sulfide radical cations and the oxyanions.

Affiliations: 1: Department of Pharmaceutical Chemistry, University of Kansas, Lawrence, KS 66047, USA; 2: Radiation Laboratory, University of Notre Dame, Notre Dame, IN 46556, USA; 3: Institute of Nuclear Chemistry and Technology, 03-195 Warsaw, Poland; 4: Faculty of Chemistry, Adam Mickiewicz University, 60-780 Poznan, Poland


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