Electrochemical sensing and imaging based on ion transfer at liquid/liquid interfaces

Amemiya, Shigeru; Kim, Jiyeon; Izadyar, Anahita; Benjamin, Kabagambe,; Shen, Mei; Ishimatsu, Ryoichi

doi:10.1016/j.electacta.2013.03.098

Cited by 55 publications

(47 citation statements)

References 149 publications

(166 reference statements)

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“…The characteristic features of a thin-layer CV without diffusional effects were ensured by using double-polymer-modified electrodes 26 in the presence of excess amounts of target ions. 16 Specifically, a thin PVC membrane was spin-coated onto a gold electrode modified with the oxidized form of a conducting polymer membrane, PEDOT-C 10 , as an efficient voltammetric ionto-electron transducer for aqueous cations.…”

Section: Resultsmentioning

confidence: 99%

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: Resultsmentioning

confidence: 99%

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

Greenawalt

Amemiya

2016

Anal. Chem.

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“…The forward and reverse transfers of the citalopram, fluoxetine, and sertraline ions into the PVC membrane were driven by the reduction and oxidation of the PEDOT-C14 film on the underlying pencil lead electrode, respectively. During the stripping cycle the oxidized state of the PEDOT-C14 film is restored and all ions transferred into the membrane phase are transferred back to the drinking water sample[12]. In agreement with this statement, the background corrected current at the end of the reverse scan approaches zero (see supplementaryFig.…”

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confidence: 76%

“…A c c e p t e d M a n u s c r i p t 12 The detection limit achieved with the pencil lead based electrode is much better than the detection limit reported in the literature for PVC-based potentiometric solid-contact ion-selective electrodes (SC-ISEs) [45]. Compared with the detection of fluoxetine with a commercial BDD electrode, the capability of the double membrane coated pencil lead sensor is a unique advantage and enabled the measurements in tap and river water [31].…”

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confidence: 99%

“…Electrochemical methods have several advantages over other analytical methods due to their simplicity and low cost. Electrochemical sensors have short response time, excellent selectivity and sensitivity, and have the capability to measure directly analytes in complex matrices [8][9][10][11][12][13][14][15]. The toxicity of selective serotonin reuptake inhibitors (SSRIs) such as fluoxetine, sertraline, and citalopram were initially reported a decade ago [16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

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Ion transfer stripping voltammetry for the detection of nanomolar levels of fluoxetine, citalopram, and sertraline in tap and river water samples

Izadyar

Arachchige

Cornwell

et al. 2016

Sensors and Actuators B: Chemical

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“…The use of pipet electrodes based on ionic transfer across an interface between two immiscible electrolyte solutions (ITIES) 28–41 has been an important method to detect ionic analytes. Ionic transfer of neurotransmitters across ITIES, mainly micro- and macrointerfaces has been reported.…”

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Nanopipet-Based Liquid–Liquid Interface Probes for the Electrochemical Detection of Acetylcholine, Tryptamine, and Serotonin via Ionic Transfer

2015

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A nanoscale interface between two immiscible electrolyte solutions (ITIES) provides a unique analytical platform for the detection of ionic species of biological interest such as neurotransmitters and neuromodulators, especially those that are otherwise difficult to detect directly on a carbon electrode without electrode modification. We report the detection of acetylcholine, serotonin, and tryptamine on nanopipet electrode probes with sizes ranging from a radius of ≈7 to 35 nm. The transfer of these analytes across a 1,2-dichloroethane/water interface was studied by cyclic voltammetry and amperometry. Well-defined sigmoidal voltammograms were observed on the nanopipet electrodes within the potential window of artificial seawater for acetylcholine and tryptamine. The half wave transfer potential, E1/2, of acetylcholine, tryptamine, and serotonin were found to be −0.11, −0.25, and −0.47 V vs E1/2,TEA (term is defined later in experimental), respectively. The detection was linear in the range of 0.25–6 mM for acetylcholine and of 0.5–10 mM for tryptamine in artificial seawater. Transfer of serotonin was linear in the range of 0.15–8 mM in LiCl solution. The limit of detection for serotonin in LiCl on a radius ≈21 nm nanopipet electrode was 77 μM, for acetylcholine on a radius ≈7 nm nanopipet electrode was 205 μM, and for tryptamine on a radius ≈19 nm nanopipet electrode was 86 μM. Nanopipet-supported ITIES probes have great potential to be used in nanometer spatial resolution measurements for the detection of neurotransmitters.

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Electrochemical sensing and imaging based on ion transfer at liquid/liquid interfaces

Cited by 55 publications

References 149 publications

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

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

Ion transfer stripping voltammetry for the detection of nanomolar levels of fluoxetine, citalopram, and sertraline in tap and river water samples

Nanopipet-Based Liquid–Liquid Interface Probes for the Electrochemical Detection of Acetylcholine, Tryptamine, and Serotonin via Ionic Transfer

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