Ion-Selective Electrodes with Unusual Response Functions: Simultaneous Formation of Ionophore–Primary Ion Complexes with Different Stoichiometries

Miyake, Masafumi; Chen, Li D.; Pozzi, Gianluca; Bühlmann, Philippe

doi:10.1021/ac202761x

Cited by 27 publications

(25 citation statements)

References 59 publications

(157 reference statements)

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“…Moreover, this is the first voltammetric demonstration of apparently super-Nernstian slopes, which were reported for the primary ion in the presence of the secondary ion in zero-current potentiometry. 21-23 By contrast, nearly Nernstian slopes of 28 ± 2 mV/decade ( N = 4) were obtained for barium ion in the absence of sodium ion as expected from eqs 12 and 15(Figure 4). …”

Section: Resultssupporting

confidence: 60%

Voltammetric Mechanism of Multiion Detection with Thin Ionophore-Based Polymeric Membrane

Greenawalt

Amemiya

2016

Anal. Chem.

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The capability to detect multianalyte ions in their mixed solution is an important advantage of voltammetry with an ionophore-based polymeric membrane against the potentiometric and optical counterparts. This advanced capability is highly attractive for the analysis of physiological ions at millimolar concentrations in biological and biomedical samples. Herein, we report on the comprehensive response mechanisms based on the voltammetric exchange and transfer of millimolar multiions at a thin polymeric membrane, where an ionophore is exhaustively depleted upon the transfer of the most favorable primary ion, IzI. With a new volt-ammetric ion-exchange mechanism, the primary ion is exchanged with the secondary favorable ion, JzJ, at more extreme potentials to transfer a net charge of |zJ|/nJ – |zI|/nI for each ionophore molecule, which forms 1:nI and 1:nJ complexes with the respective ions. Alternatively, an ion-transfer mechanism utilizes the second ionophore that independently transfers the secondary ion without ion exchange. Experimentally, a membrane is doped with a Na+- or Li+-selective ionophore to detect not only the primary ion, but also the secondary alkaline earth ion based on the ion-exchange mechanism, where both ions form 1:1 complexes with the ionophores to transfer a net charge of +1. Interestingly, the resultant peak potentials of the secondary divalent ion vary with its sample activity to yield an apparently super-Nernstian slope as predicted theoretically. By contrast, the voltammetric exchange of calcium ion (nI = 3) with lithium ion (nJ = 1) by a Ca2+-selective ionophore is thermodynamically unfavorable, thereby requiring a Li+-selective ionophore for the ion-transfer mechanism.

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Section: Resultssupporting

confidence: 60%

Voltammetric Mechanism of Multiion Detection with Thin Ionophore-Based Polymeric Membrane

Greenawalt

Amemiya

2016

Anal. Chem.

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“…The nanocomposite-based sensors showed a super-high Nernstian slope value (75.3 mV/decade). This anomalous high response has been already reported for chelating ionophores, such as crown ethers [41]. However, the data reported in the same plot in the presence of Na + evidenced clearly that is not possible to discriminate between the two ions.…”

Section: Electrochemical Studiessupporting

confidence: 70%

Electrochemical and Fluorescent Properties of Crown Ether Functionalized Graphene Quantum Dots for Potassium and Sodium Ions Detection

et al. 2021

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The concentration of sodium and potassium ions in biological fluids, such as blood, urine and sweat, is indicative of several basic body function conditions. Therefore, the development of simple methods able to detect these alkaline ions is of outmost importance. In this study, we explored the electrochemical and optical properties of graphene quantum dots (GQDs) combined with the selective chelating ability of the crown ethers 15-crown-5 and 18-crown-6, with the final aim to propose novel composites for the effective detection of these ions. The results obtained comparing the performances of the single GQDs and crown ethers with those of the GQDs-15-crown-5 and GQDs-18-crown-6 composites, have demonstrated the superior properties of these latter. Electrochemical investigation showed that the GQDs based composites can be exploited for the potentiometric detection of Na+ and K+ ions, but selectivity still remains a concern. The nanocomposites showed the characteristic fluorescence emissions of GQDs and crown ethers. The GQDs-18-crown-6 composite exhibited ratiometric fluorescence emission behavior with the variation of K+ concentration, demonstrating its promising properties for the development of a selective fluorescent method for potassium determination.

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“…21 The mPD/SPD (50/50) copolymer microparticles containing the most sulfonic groups show the sub Nernstian response to Pb(II) because the amino/imino/sulfonic groups on the copolymer chains with the lowest molecular weight caused by the presence of too many sulfonic groups as ionophores would form complexes of the lowest stoichiometries. 22 In particular, the mPD/SPD (95/5) copolymer microparticles yield the best detection limit down to 1.26 Â 10 À7 M possibly due to their highest electrical conductivity and the smallest elementary particles, as mentioned earlier. 20 It is apparent that this potentiometric Pb(II)-sensor or -ISE demonstrates superior detection limit than the other ones in the externally plasticized PVC membrane with the detection limit of only at 10 À7 to 10 À5 M orders of magnitude summarized in Table 2.…”

Section: Effect Of Mpd/spd Copolymer Composition On the Pb(ii)sensormentioning

confidence: 69%

Lead-ion potentiometric sensor based on electrically conducting microparticles of sulfonic phenylenediamine copolymer

Huang

Ding

2013

Analyst

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A potentiometric sensor to detect lead ions using newly synthesized conducting copolymer microparticles as an ionophore in self-supporting poly(vinyl chloride) membrane matrix plasticized with dioctyl phthalate was developed. The copolymer microparticles containing many ligating functional groups including amino, imino and sulfonic groups were synthesized by a chemical oxidative copolymerization of m-phenylenediamine (mPD) and p-sulfonic-m-phenylenediamine (SPD) in pure water. Due to the presence of -NH-, -N=, -NH2, and -SO3H ligating groups on the microparticles, a linear Nernstian response is obtained within a Pb(II) activity range from 1.00 × 10(-6) M to 1.00 × 10(-3) M. The Pb(II)-sensor containing the mPD/SPD (95/5) copolymer microparticles with the maximal electrical conductivity demonstrates a superior detection limit down to 1.26 × 10(-7) M, short response time to 14 s, and long lifetime of up to 4 months. The Pb(II)-sensor also exhibits a selective response to Pb(II) over 9 other metal ions and a pH independent plateau between 2.7 and 5.0. These advantages could make for a robust sensor performing credible analysis of Pb(II) concentration in real-world samples at trace levels.

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Ion-Selective Electrodes with Unusual Response Functions: Simultaneous Formation of Ionophore–Primary Ion Complexes with Different Stoichiometries

Cited by 27 publications

References 59 publications

Voltammetric Mechanism of Multiion Detection with Thin Ionophore-Based Polymeric Membrane

Voltammetric Mechanism of Multiion Detection with Thin Ionophore-Based Polymeric Membrane

Electrochemical and Fluorescent Properties of Crown Ether Functionalized Graphene Quantum Dots for Potassium and Sodium Ions Detection

Lead-ion potentiometric sensor based on electrically conducting microparticles of sulfonic phenylenediamine copolymer

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