Characterization of Partially Sulfonated Polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene Thin Films for Spectroelectrochemical Sensing

Pantelić, Nebojša; Andria, Sara E.; Heineman, William R.; Seliskar, Carl J.

doi:10.1021/ac900765t

Cited by 21 publications

(25 citation statements)

References 36 publications

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“…Partially sulfonated polymers (e.g., Nafion, polystyrene sulfonate (PSS) and polystyrene-block-poly(ethylene-ran-butylene)-blockpolystyrene (SSEBS), shown in Figure 4 , take up bulky positively charged cations. Both SSEBS and Nafion have demonstrated the ability to preconcentrate a range of cations, both organic (e.g., phenosafranine and rhodamine 6G) and inorganic coordination compounds (e.g., [Ru(bpy) 3 ] 2 + , [Fe(bpy) 3 ] 2 + , [Cu(bpy) 2 ] 2 + ) ( Ross et al 2000, Andria et al 2004, Pantelic and Seliskar 2007Pantelic et al 2006Pantelic et al , 2009. More importantly, the spectroscopic properties (luminescence intensity and emission life-times) of these compounds are not destroyed or significantly reduced by the films upon their entrapment and can be exploited for their detection and modulation.…”

Section: Choice and Development Of Polymer Filmsmentioning

confidence: 99%

Three-component spectroelectrochemical sensor module for the detection of pertechnetate (TcO4-)

Chatterjee

Bryan

Seliskar

et al. 2013

Reviews in Analytical Chemistry

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This review looks at the advancements in the development of a sensor for technetium (Tc) that is applicable to characterizing and monitoring the vadose zone and associated subsurface water. Subsurface contamination by Tc is of particular concern for two reasons: the long lifetime of its most common isotope 99 Tc (half-life = 2 × 10 5 years) and the fast migration in soils of pertechnetate (TcO 4 -), which is considered to be the dominant 99 Tc species in ground water. TcO 4 -does not have a characteristic spectral signature which prevents its rapid, sensitive, and economic in situ detection. To address this problem, a novel spectroelectrochemical sensor has been designed, that combines three modes of selectivity (electrochemistry, spectroscopy, and selective partitioning) into a single sensor to substantially improve specificity, which is critical in the specific detection of an analyte in the presence of potential interfering species. The sensor consists of a basic spectroelectrochemical configuration: a waveguide with an optically transparent electrode (OTE) that is coated with a thin chemically-selective film that preconcentrates the analyte. The key to adapting this generic sensor to detect TcO 4 -and Tc complexes lies in the development of chemically-selective films that preconcentrate the analyte and, when necessary, chemically convert it into a complex with electrochemical and spectroscopic properties appropriate for sensing. The chemically selective films can be combined with ligands which are capable of reacting with TcO 4 -to form coordination complexes, the spectral properties of which can be used to enhance the sensitivity of detection. The first half of this review describes the general concept of the sensor and the rationale for the selection of its specific components, and the development and characterization of the sensor for the different detection modules. The second half summarizes the synthesis and characterization of complexes relevant for the detection of technetium, and the progress in the utilization of the sensor module for the effective detection of these complexes.

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Section: Choice and Development Of Polymer Filmsmentioning

confidence: 99%

Three-component spectroelectrochemical sensor module for the detection of pertechnetate (TcO4-)

Chatterjee

Bryan

Seliskar

et al. 2013

Reviews in Analytical Chemistry

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“…Films that have been used in the sensor include QPVP (quaternized poly(4-vinyl pyridine)), 24,25 PDMDAAC (poly(dimethyl diallylammonium chloride)), PVTAC (poly(vinyl tetraammonium chloride), 26 Nafion, 23 partially sulfonated polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene, (SSEBS), 27 and sol-gel composites of QPVP, PDMDAAC, PVTAC and Nafion with SiO 2 . Choice of material for the film determines the selectivity of the film for the analyte relative to other components of the solution.…”

Section: Chemically Selective Filmsmentioning

confidence: 99%

“…15,17,23,27,37 The flow rate of solution through the flow cell was controlled with a syringe pump. Electrochemical potentials were measured versus a Ag/AgCl (3M NaCl) reference microelectrode (Cypress Systems) positioned at the center back of the cell.…”

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confidence: 99%

Spectroelectrochemistry as a strategy for improving selectivity of sensors for security and defense applications

Heineman¹,

Seliskar²,

Morris³

et al. 2012

SPIE Proceedings

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Spectroelectrochemistry provides improved selectivity for sensors by electrochemically modulating the optical signal associated with the analyte. The sensor consists of an optically transparent electrode (OTE) coated with a film that preconcentrates the target analyte. The OTE functions as an optical waveguide for attenuated total reflectance (ATR) spectroscopy, which detects the analyte by absorption. Alternatively, the OTE can serve as the excitation light for fluorescence detection, which is generally more sensitive than absorption. The analyte partitions into the film, undergoes an electrochemical redox reaction at the OTE surface, and absorbs or emits light in its oxidized or reduced state. The change in the optical response associated with electrochemical oxidation or reduction at the OTE is used to quantify the analyte. Absorption sensors for metal ion complexes such as [Fe(CN) 6 ] 4-and [Ru(bpy) 3 ] 2+ and fluorescence sensors for [Ru(bpy) 3 ] 2+ and the polycyclic aromatic hydrocarbon 1-hydroxypyrene have been developed. The sensor concept has been extended to binding assays for a protein using avidin-biotin and 17β-estradiol-anti-estradiol antibodies. The sensor has been demonstrated to measure metal complexes in complex samples such as nuclear waste and natural water. This sensor has qualities needed for security and defense applications that require a high level of selectivity and good detection limits for target analytes in complex samples. Quickly monitoring and designating intent of a nuclear program by measuring the Ru/Tc fission product ratio is such an application.

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“…32,35 It has been reported in literature that SSEBS is capable of uptaking positively charged analytes while repelling negatively charged interferences. 32,35 ITO has been used for spectroelectrochemical stripping voltammetry where an optical change associated with the stripping of preconcentrated metal is used as the analytical signal. 37–39 However, neither bare ITO nor SSEBS coated ITO have ever been used as an electrode material for CSV of Mn 2+ .…”

Section: Introductionmentioning

confidence: 99%

Bare and Polymer-Coated Indium Tin Oxide as Working Electrodes for Manganese Cathodic Stripping Voltammetry

et al. 2016

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Though an essential metal in the body, manganese (Mn) has a number of health implications when found in excess that are magnified by chronic exposure. These health complications include neurotoxicity, memory loss, infertility in males, and development of a neurologic psychiatric disorder- manganism. Thus, trace detection in environmental samples is increasingly important. Few electrode materials are able to reach the negative reductive potential of Mn required for anodic stripping voltammetry (ASV), so cathodic stripping voltammetry (CSV) has been shown to be a viable alternative. We demonstrate Mn CSV using an indium tin oxide (ITO) working electrode both bare and coated with a sulfonated charge selective polymer film, polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene-sulfonate (SSEBS). ITO itself proved to be an excellent electrode material for Mn CSV, achieving a calculated detection limit of 5 nM (0.3 ppb) with a deposition time of 3 min. Coating the ITO with the SSEBS polymer was found to increase the sensitivity and lower the detection limit to 1 nM (0.06 ppb). This polymer modified electrode offers excellent selectivity for Mn as no interferences were observed from other metal ions tested (Zn2+, Cd2+, Pb2+, In3+, Sb3+, Al3+, Ba2+, Co2+, Cu2+, Ni3+, Bi3+, and Sn2+) except Fe2+, which was found to interfere with the analytical signal for Mn2+ at a ratio 20:1 (Fe2+:Mn2+). The applicability of this procedure to the analysis of tap, river, and pond water samples was demonstrated. This simple, sensitive analytical method using ITO and SSEBS-ITO could be applied to a number of electroactive transition metals detectable by CSV.

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Characterization of Partially Sulfonated Polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene Thin Films for Spectroelectrochemical Sensing

Cited by 21 publications

References 36 publications

Three-component spectroelectrochemical sensor module for the detection of pertechnetate (TcO4-)

Three-component spectroelectrochemical sensor module for the detection of pertechnetate (TcO4-)

Spectroelectrochemistry as a strategy for improving selectivity of sensors for security and defense applications

Bare and Polymer-Coated Indium Tin Oxide as Working Electrodes for Manganese Cathodic Stripping Voltammetry

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