Optical chloride sensor based on dimer-monomer equilibrium of indium(III) octaethylporphyrin in polymeric film

A novel transduction chemistry for preparing optical anion-selective polymeric films that respond reversibly and selectively to chloride ion activity is demonstrated. The chloride sensors are prepared by casting thin (5-10 microm) plasticized PVC films containing indium(III) octaethylporphyrin hydroxide, along with optimized levels of a lipophilic tetraphenylborate salt, onto glass slides. When bathed in low-pH buffered solutions void of chloride, the porphyrin species spontaneously forms a hydroxide ion-bridged dimer, with the added lipophilic borate species serving as the counteranion for this complex. The maximum for the Soret absorption band of this dimeric species is shifted to 390 nm, from 410 nm for the initial monomeric porphyrin. Increases in chloride ion levels in the bathing solution results in chloride extraction and ligation to the In(III) center, and concomitant breaking of the dimer into monomeric porphyrin species, yielding a decrease in absorbance at 390 nm and an increase in optical signal at 410 nm. Under optimized conditions, optical selectivity coefficients toward chloride over a wide range of other anions (NO3-, ClO4-, SCN-, SO4(2-), F-, Br-, H2PO4-) are measured to be < 10(-3). Of all anions tested, only salicylate yields a slightly greater response than chloride. This selectivity is shown to be adequate for reversible and accurate sensing of chloride levels in diluted serum samples.