title: Luminescence-based spectroelectrochemical sensor for [Tc(dmpe)3]2+/+ (dmpe = 1,2-bis(dimethylphosphino)ethane) within a charge-selective polymer film.
abstract: A spectroelectrochemical sensor consisting of an indium tin oxide (ITO) optically transparent electrode (OTE) coated with a thin film of partially sulfonated polystyrene-blockpoly(ethylene-ran-butylene)-block-polystyrene (SSEBS) was developed for [Tc(dmpe)(3)](+) (dmpe = 1,2-bis(dimethylphosphino)ethane). [Tc(dmpe)(3)](+) was preconcentrated by ion-exchange into the SSEBS film after a 20 min exposure to aqueous [Tc(dmpe)(3)](+) solution, resulting in a 14-fold increase in cathodic peak current compared to a bare OTE. Colorless [Tc(dmpe)(3)](+) was reversibly oxidized to colored [Tc(dmpe)(3)](2+) by cyclic voltammetry. Detection of [Tc(dmpe)(3)](2+) was accomplished through emission spectroscopy by electrochemically oxidizing the complex from nonemissive [Tc(dmpe)(3)](+) to emissive [Tc(dmpe)(3)](2+). The working principle of the sensor consisted of electrochemically cycling between nonemissive [Tc(dmpe)(3)](+) and emissive [Tc(dmpe)(3)](2+) and monitoring the modulated emission (λ(exc) = 532 nm; λ(em) = 660 nm). The sensor gave a linear response over the concentration range of 0.16-340.0 μM of [Tc(dmpe)(3)](2+/+) in aqueous phase with a detection limit of 24 nM.
authors.affiliation: Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.
authors.forename: Sayandev
authors.initials: S
authors.lastname: Chatterjee
authors.forename: Andrew S
authors.initials: AS
authors.lastname: Del Negro
authors.forename: Matthew K
authors.initials: MK
authors.lastname: Edwards
authors.forename: Samuel A
authors.initials: SA
authors.lastname: Bryan
authors.forename: Necati
authors.initials: N
authors.lastname: Kaval
authors.forename: Nebojsa
authors.initials: N
authors.lastname: Pantelic
authors.forename: Laura K
authors.initials: LK
authors.lastname: Morris
authors.forename: William R
authors.initials: WR
authors.lastname: Heineman
authors.forename: Carl J
authors.initials: CJ
authors.lastname: Seliskar