ON THE EFFICIENCY OF METHYLENE-BLUE VERSUS PERSULFATE CATALYSIS OF POLYACRYLAMIDE GELS, AS INVESTIGATED BY CAPILLARY ZONE ELECTROPHORESIS

The efficiency of a novel method of photopolymerization, based on photoinitiating the reaction with methylene blue (MB), in presence of a redox couple (sodium toluenesulfinate and diphenyliodonium chloride), vs. the conventional persulfate - N,N,N',N'-tetramethylethylenediamine redox couple was investigated as a function of different effectors in solution. Oxygen dissolved in the gelling mixture strongly quenches persulfate catalysis, while leaving essentially unaltered the process initiated by photopolymerization. On the contrary, the presence of 8 M urea substantially accelerates a persulfate-driven reaction, boosting the conversion of monomers to near completion (> 98%) while leaving the photopolymerization process largely unaffected. Polyacrylamide polymerization has also been performed in a number of hydroorganic solvents (all in a 50 : 50 v/v ratio): dimethyl sulfoxide (DMSO), tetramethyl-urea, formamide and dimethylformamide. In all cases, the persulfate-catalyzed reaction was strongly quenched and even completely inhibited (in DMSO), whereas the photopolymerization process was essentially unaffected by any of these organic solvents. The reaction kinetics of the methylene blue-driven reaction could not be ameliorated when admixing an anionic dye (e.g., eosin Y) to the cationic MB, even when amply changing their molar ratios. Thus, it appears that photocatalysis with MB (and the redox couple sodium toluenesulfinate and diphenyliodonium chloride) is a unique process, proceeding at optimum rate under the most adverse conditions, completely insensitive to any kind of positive and negative effectors and able to ensure at least 95% monomer conversion under the standard conditions of 1 h reaction time at room temperature. Due to the fact that the MB system is also unaffected by the pH of the gelling solution (in the pH 4-10 interval), it would appear that such a system is largely superior to any other catalyst mixture so far proposed in the field of polyacrylamide catalysis.