Phenoxy-substituted boron subphthalocyanine as a ionophore of ion-selective electrodes

Abstract

Phenoxy-substituted boron subphthalocyanine was synthesized and studied as an ionophore of plasticized polyvinyl chloride membranes of ion-selective electrodes. The electrodes exhibit reversible response to dobutamine, demonstrating the cation function, as well as reversible response to the salicylate anion. The effects of concentration of the ionophore (0.2–5 wt %) and ionic components (sodium tetraphenylborate, TPhBNa, and tributylhexadecylphosphonium bromide, TBGDPBr), including ionic liquids (ILs), such as diphenylbutylethylphosphonium bis(triflyl)imide, diphenylbutylethylphosphonium hexafluorophosphate, and 1,3-dihexadecylimidazolium chloride, as well as plasticizers, such as ortho-nitrophenyloctyl ether and diethyl sebacate, on the electrochemical characteristics of membranes were studied. For the electrode containing 2% of the phenoxy-substituted boron subphthalocyanine in dobutamine and salicylate solutions, the slopes of the electrode function were 36 ± 1 mV/dec and–46 ± 3 mV/dec and the limits of detection (LODs) were 4 × 10–5 M and 3 × 10–4 M, respectively. The addition of an ionic liquid containing the diphenylbutylethylphosphonium cation and the bis(triflyl)imide and hexaflurophosphate anions to the membrane composition had no effect on the response of membrane electrodes to both dobutamine and salicylate. The use of phenoxy-substituted boron subphthalocyanine in an amount of 2% and the TPhBNa additive significantly improved sensor characteristics: the slope of the electrode function (S) for the dobutamine-selective electrode was (54 ± 1) mV/dec and LOD was 1 × 10–5 M. Dobutamine can be determined in the presence of dopamine, adrenalin, and glucose. Electrodes based on 2% phenoxy-substituted boron subphthalocyanine and 0.5% (C16H33)2ImCl, or TBGDPBr in salicylate solutions demonstrate the slope of the electrode function close to the theoretical one and a low limit of detection: S = (–59 ± 1) mV/dec, LOD = 2 × 10–5 M and S = (–57 ± 1) mV/dec, LOD = 4 × 10–5 M, respectively. The anti-Hofmeister selectivity of sensors was observed. The electrode based on phenoxy-substituted boron subphthalocyanine and (C16H33)2ImCl was used for the assay of acetylsalicylic acid in the drug Cardiomagnyl.