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Takayo Moriuchi-Kawakami, Akihisa Higashikado, Masanari Hirahara, Keiichi Fujimori, Toshiyuki Moriuchi, Oxovanadium(IV) heteromacrocyclic complexes as ionophores for iodide-selective electrodes, Chemistry Letters, Volume 53, Issue 4, April 2024, upad058, https://doi.org/10.1093/chemle/upad058
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Abstract
Highly selective poly(vinyl chloride) (PVC) membrane electrodes, based on oxovanadium(IV) complexes of heteromacrocyclic compounds as new iodide-selective ionophores for ion-selective electrodes (ISEs), were fabricated with a composition of PVC (28.1 wt%), plasticizers (69.3 wt%), ionophores (2.6 wt%), and cation excluders (15 mol% relative to the ionophore). The electrode prepared from oxovanadium(IV) tetraphenyl porphyrin with 2-nitrophenyl octyl ether (o-NPOE) as the membrane solvent and tetradodecylammonium chloride (TDDACl) as the cation excluder was found to exhibit the best sensitivity over a wide concentration range from 5.0 × 10–7 to 2.1 × 10–2 M with a Nernstian response of −59.02 mV per decade and the highest ion-selectivity toward I− ions over perchlorate ions (I−/ClO4− = 91).

Heteromacrocyclic complexes of vanadium(IV) oxide were developed as ionophores for ionselective electrodes (ISEs). The ISE based on oxovanadium(IV) tetraphenyl porphyrin using o-NPOE as the membrane solvent and TDDACl as the cation excluders was found to exhibit the best sensitivity toward the I- ions over a wide concentration range with a Nernstian response and the highest ion-selectivity toward the I- ions over perchlorate ions.