Electrochemical detection of peroxynitrite using hemin-PEDOT functionalized boron-doped diamond microelectrode.

Peroxynitrite is a potent nitroxidation agent and highly reactive metabolite, clinically correlated with a rich pathophysiology. Its sensitive and selective detection is challenging due to its high reactivity and short sub-second lifetime. Boron-doped diamond (BDD) microelectrodes have attracted interest because of their outstanding electroanalytical properties that include a wide working potential window and enhanced signal-to-noise ratio. Herein, we report on the modification of a BDD microelectrode with an electro-polymerized film of hemin and polyethylenedioxythiophene (PEDOT) for the purpose of selectively quantifying peroxynitrite. The nanostructured modified polymer layer was characterized by Raman spectroscopy and scanning electron microscopy (SEM). The electrochemical response to peroxynitrite was studied by voltammetry and time-based amperometry. The measured detection limit was 10 ± 0.5 nM (S/N = 3), the sensitivity was 4.5 ± 0.5 nA nM(-1) and the response time was 3.5 ± 1 s. The hemin-PEDOT BDD sensors exhibited a response variability of 5% or less (RSD). The stability of the sensors after a 20-day storage in 0.1 M PB (pH 7.4) at 4 °C was excellent as at least 93% of the initial response to 50 nM PON was maintained. The presence of PEDOT was correlated with a sensitivity increase.

Nanostructured poly(3,4-ethylenedioxythiophene)-metalloporphyrin films: improved catalytic detection of peroxynitrite.

We investigated in this paper the sensing performance of inherently conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with hemin (iron protoporphyrin) as an electrocatalytic reporter. The sensing platform is prepared by electrodeposition of a composite film of hemin-PEDOT on a 30-microm diameter carbon fiber electrode (CFE). The polymerized films were characterized by field emission scanning electron microscopy (FESEM), which pointed to nanostructured films with tortuous pores. The electrocatalytic oxidation of peroxynitrite was characterized by cyclic voltammetry as well as other electrochemical methods. The catalytic current is proportional to the analyte's concentration. Optimized hemin-PEDOT modified CFEs were utilized for the first time to detect ONO2(-), with a response time down to 5 s and a limit of detection as low as 200 nM as evidenced by amperometry. Our hemin-PEDOT modified CFEs have a sensitivity of 13 nA/microM, ca.130 times higher than the bare CFE. More work is underway using other metalloporphyrins as electrocalalysts to improve the detection limit, the selectivity, and to further miniaturize these hemin-PEDOT modified electrodes.

Polymerized crystalline colloidal array chemical-sensing materials for detection of lead in body fluids.

We have developed intelligent polymerized crystalline colloidal array (IPCCA) chemical-sensing materials for detection of Pb(2+) in high ionic-strength environments such as body fluids with a detection limit of <500 nmol L(-1) Pb(2+) (100 ppb). This IPCCA lead sensor consists of a mesoscopically periodic array of colloidal particles polymerized into an acrylamide hydrogel. The array Bragg-diffracts light in the visible spectral region because of the periodic spacing of the colloidal particles. This material also contains a crown ether chelating agent for Pb(2+). Chelation of Pb(2+) by the IPCCA in low-ionic-strength solutions results in a Donnan potential that swells the gel, which red-shifts the diffracted light in proportion to the Pb(2+) concentration. At high ionic strength the Donnan potential is, unfortunately, swamped and no static response occurs for these sensors. We demonstrate, however, that we can determine Pb(2+) at high ionic strength by incubating these IPCCA in a sample solution and then measuring their transient response on exposure to pure water. The non-complexed ions diffuse from the IPCCA faster than the bound Pb(2+). The resulting transient IPCCA diffraction red-shift is proportional to the concentration of Pb(2+) in the sample. These IPCCA sensors can thus be used as sensing materials in optrodes to determine Pb(2+) in high-ionic-strength solutions such as body fluids.