No abstract

Pt electrodes of different sizes (2 × 10 -5 -2 × 10 -2 cm 2 ) and geometries (disks and cylinders) were coated with the ultrathin non-conducting form of poly(o-phenylenediamine), PPD, using amperometric electrosynthesis. Analysis of the ascorbic acid (AA) and H 2 O 2 apparent permeabilities for these Pt/PPD sensors revealed that the PPD deposited near the electrode insulation (Teflon or glass edge) was not as effective as the bulk surface PPD for blocking AA access to the Pt substrate. This discovery impacts on the design of implantable biosensors where electrodeposited polymers, such as PPD, are commonly used as the permselective barrier to block electroactive interference by reducing agents present in the target medium. The undesirable "edge effect" was particularly marked for small disk electrodes which have a high edge density (ratio of PPDinsulation edge length to electrode area), but was essentially absent for cylinder electrodes with a length of >0.2 mm. Sample biosensors, with a configuration based on these findings (25 µm diameter Pt fiber cylinders) and designed for brain neurotransmitter L-glutamate, behaved well in vitro in terms of Glu sensitivity and AA blocking.The design of biosensors for implantation in functioning biological tissues is an important area of research with significant socioeconomic impact. 1-4 Depending on the target analyte, different signal transduction pathways have been exploited in the design of enzyme-based biosensors, including direct oxidation of reduced oxidases, 5-7 dehydrogenase chemistries, 8-10 redox mediators, 11-13 and spectrophotometric approaches. 14-16 However, "first generation" electrochemical biosensors, based on reactions 1-3, remain the most common design for many applications. 1,2,[17][18][19] The majority of these are oxidase-based devices designed to operate in amperometric mode, detecting H 2 O 2 generated by the reaction of the co-substrate (dioxygen) with the reduced form of the enzyme.First-generation biosensors in general, and especially those designed for tissue implantation, 20-24 must be capable of effective rejection of electroactive interference by endogenous reducing agents in the target medium because these devices are normally operated at a high applied overpotential for efficient H 2 O 2 * To whom correspondence should be addressed. E-mail: robert.oneill@ucd.ie.