TITLE:
Solid-Contact Perchlorate Sensor with Nanomolar Detection Limit Based on Cobalt Phthalocyanine Ionophores Covalently Attached to Polyacrylamide
AUTHORS:
Mohammad Nooredeen Abbas, Abdel Lattief A. Radwan, Philippe Bühlmann, Mahmud A. Abd El Ghaffar
KEYWORDS:
Ion-Selective Electrode, Solid Contact, Covalent Ionophore Attachment, Perchlorate, Flow-Injection Analysis, Urine
JOURNAL NAME:
American Journal of Analytical Chemistry,
Vol.2 No.7,
November
3,
2011
ABSTRACT: Novel solid-contact perchlorate sensors based on cobalt phthalocyanine-C-monocarboxylic acid (I), and cobalt phthalocyanine-C,C,C,C-tetracarboxylic acid (II) as free ionophores and covalently attached to polyacryla- mide (PAA)—ionophores III and IV, respectively were prepared. The all solid-state sensors were constructed by the application of a thin film of a polymer cocktail containing a phthalocyanine ionophore and cetyltrimethylammonium bromide (CTMAB) as a lipophilic cationic additive onto a gold electrode precoated with the conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) as an ion and electron transducer. The sensor with 10.3% of ionophore (III) covalently attached to plasticizer-free poly (butyl methacrylate-co-do- decyl methacrylate) (PBDA) exhibited a good selectivity for perchlorate and discriminated many ions, in- cluding F–, Cl–, Br–, I–, SCN–, , S2– and . The covalent attachment of the ionophore to the polymer resulted in a near-Nernstian anionic slope of –62.3 mV/decade whereas a super-Nernstian slope of –79.9 mV/ decade was obtained for the free ionophore. The sensor covered a linear concentration range of 5 × 10–9 - 1 × 10–2 mol?L–1 with a lower detection limit (LDL) of 1 × 10–9 mol?L–1 and gave a stable response over a pH range of 4 - 10.5. The all-solid state sensors were utilized for the selective flow injection potentiometric determination of perchlorate in natural water and human urine samples in the nanomolar concentration range.