Luminescence-Based Spectroelectrochemical Sensor for [Tc(dmpe)3]2+/+ (dmpe = 1,2-bis(dimethylphosphino)ethane) within a Charge-Selective Polymer Film

Chatterjee, Sayandev; Negro, Andrew S. Del; Edwards, Matthew K.; Bryan, Samuel A.; Kaval, Necati; Pantelić, Nebojša; Morris, Laura K.; Heineman, William R.; Seliskar, Carl J.

doi:10.1021/ac1030368

Cited by 34 publications

(40 citation statements)

References 32 publications

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“…This indicates the electrochemical reaction is diffusion-controlled [4]. Furthermore, scan rate studies did not indicate the presence of any side reactions or loss of complex, which suggests the system undergoes a simple electrochemical mechanism.…”

Section: Electrochemical Characterizationmentioning

confidence: 90%

“…By monitoring analytes with both electrochemistry and spectroscopy, spectroelectrochemistry demonstrates a powerful capability to offer multiple levels of selectivity for a desired analyte [3,4]. The technique can isolate and identify analyte signatures by probing both select potential ranges and select wavelength ranges in either absorption or emission modes [5,6].…”

Section: Introductionmentioning

confidence: 99%

“…It is therefore necessary to select ligands that not only have the appropriate energetics to sensitize Eu fluorescence but also are electrochemically inactive in the potential range of interest [4,18]. To satisfy electrochemical needs, 2,2'-bipyridine (bpy) and bpy derivatives were chosen as the focus of this work [18].…”

Section: Introductionmentioning

confidence: 99%

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Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

et al. 2016

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Fast, cost effective, and robust means of detecting and quantifying lanthanides are needed to support more efficient tracking within the nuclear, medicinal, and industrial fields. Furthermore, methods for isolating lanthanide signal from spectroscopic interferents are also needed. Applying spectroelectrochemistry to the detection of these species can meet those needs. However, application of this technique is limited by the low molar absorptivities and quantum yields of the lanthanides. These limitations can be circumvented by complexing the lanthanides with sensitizing ligands that enhance fluorescence, thereby dropping the limits of detection. Complexation will also cause changes in the electrochemical behavior of the lanthanides. To demonstrate this concept, studies were completed using europium as a model lanthanide in complexes with four different sensitizing ligands, which included 2,2′‐bipyridine and related derivatives. Results indicate that all four studied complexes demonstrate quasi‐reversible redox couples and improvements in limits of detection where electrochemical and spectroscopic characteristics showed some dependence on attached ligand. All four complexes studied display the necessary characteristics for spectroelectrochemical analysis, which was successfully and reproducibly applied to all Eu complexes.

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Section: Electrochemical Characterizationmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

et al. 2016

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“…By contrast, in the species exhibiting emission properties, the limit of detection can be significantly lowered. Therefore, redox active luminescent probes such as [Ru(bpy) 3 ] 2 + (where bpy = 2,2 ′ -bipyridine) and [Re(dmpe) 3 ] 2 + allow for the direct detection of the analyte as low as ∼ 10 -10 -10 -13 m ( Chatterjee et al 2011b, Kaval et al 2003. With improvements in the collection and excitation optics of the cell, even lower detection limits are possible.…”

Section: Three Component Sensormentioning

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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“…Re and Tc compounds generally have nearly identical chemical properties, [43][44][45][46][47][48] making Re an acceptable non-radioactive analogue for 99 Tc, which has no non-radioactive isotopes. We subsequently demonstrated the ability to directly sense Tc using the spectroelectrochemical sensor technique for the [Tc(dmpe) 3 ] + complex 49 . After partitioning into the sensor film, [Tc(dmpe) 3 ] + can be reversibly oxidized to [Tc(dmpe) 3 ] 2+ , followed by fluorescence based detection at the nanomolar level in aqueous solution.…”

Section: Stored Radioactive Waste and Surrounding Ground Watermentioning

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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Luminescence-Based Spectroelectrochemical Sensor for [Tc(dmpe)₃]^2+/+ (dmpe = 1,2-bis(dimethylphosphino)ethane) within a Charge-Selective Polymer Film

Cited by 34 publications

References 32 publications

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

Electrochemistry and Spectroelectrochemistry of Luminescent Europium Complexes

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

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