Selective Permeation of Hydrogen Peroxide through Polyelectrolyte Multilayer Films and Its Use for Amperometric Biosensors

Abstract

A platinum electrode was coated with polyelectrolyte multilayer (PEM) films to prepare an amperometric hydrogen peroxide sensor which can be used in the presence of possible interferences such as ascorbic acid, uric acid, and acetaminophen. The PEM films were prepared on the surface of a Pt disk electrode by an alternate deposition of polycation and polyanion from the aqueous solutions through electrostatic force of attraction. The Pt electrodes coated with a poly(allylamine)/poly(vinyl sulfate) or poly(allylamine)/poly(styrenesulfonate) film were used successfully for detecting H2O2 selectively in the presence of the possible interfering agents. It was suggested that H2O2 can diffuse into the PEM film smoothly while the ascorbic acid, uric acid, and acetaminophen cannot penetrate the film by a size exclusion mechanism. On the other hand, the electrodes coated with PEM films containing poly(ethyleneimine) or poly(diallyldimethylammonium chloride) were not useful for the selective determination of H2O2. The results were rationalized based on the different permeability of the films due to the different molecular density or packing in the PEM films. The PEM film-coated electrode was useful for constructing glucose biosensors by coupling with glucose oxidase.

Layer-by-layer Thin Films and Microcapsules for Biosensors and Controlled Release

“…56 Amperometric uric acid sensors were also prepared using a uricase-modified electrode with a PAH-PVS LbL film. 57 The uric acid sensor exclusively detected H2O2 produced by the uricase-catalyzed reaction of uric acid, whereas the direct oxidation of uric acid on the electrode surface, which could produce a bias signal, was prevented by the PAH-PVS film.…”

“…The size exclusion effects of the LbL films depend on the type of film components; LbL films composed of PEI-PVS and PDDA-PVS pairs were less effective in excluding the oxidizable compounds. 56 Yabuki has recently discussed the size exclusion effects of polyion complex (PIC) films that were prepared by mixing polycation and polyanion solutions. 58 The PIC films composed of poly(L-lysine) and PSS exhibited size exclusion for organic compounds with a molecular weight higher than ~100, and it was H2O2-permeable.…”

Polyelectrolyte Complex Membranes for Immobilizing Biomolecules, and Their Applications to Bio-analysis

“…In fact, electrochemical interferants such as L-ascorbic acid (vitamin C), uric acid, and acetaminophen may obscure the accurate measurements of food and body fluid samples. Applying LBL 51 and PIC 9,10,36 membranes to the bio-sensing systems obviates this problem by decreasing the interfering current, and thereby lowering the detection limit of analytes by improving the signal-to-noise ratio (S/N). On this basis, we have developed biosensors for glucose, 9,45,52 ethanol, 53 L-lactate, 36,44,54 L-glutamate, 55,56 pyruvate, 57 NADH (reduced form of nicotinamide adenine dinucleotide), 58 acetylcholine, 59 L-amino acids, 60 and D-amino acids 61 by immobilizing the respective oxidases on PIC membranes.…”

The efficiency of immobilised glutamate oxidase decreases with surface enzyme loading: an electrostatic effect, and reversal by a polycation significantly enhances biosensor sensitivity

“…These values were therefore pooled: 100 ¡ 3 nA cm 22 mM 21 , n = 23. In an attempt to increase the sensitivity further, a layer-by-layer approach described in the literature for the fabrication of sensors using a variety of polyelectrolytes [48][49][50][51] was investigated. This was found not to be advantageous here because the deposition of polycationic PEI over the polyanionic enzyme led to a marked loss of Glu sensitivity, presumably due to the large size of PEI molecules relative to GluOx (see Fig.…”