Monolayer-protected nanoparticle doped xerogels as functional components of amperometric glucose biosensors.

First-generation amperometric glucose biosensors incorporating alkanethiolate-protected gold nanoparticles, monolayer protected clusters (MPCs), within a xerogel matrix are investigated as model systems for nanomaterial-assisted electrochemical sensing strategies. The xerogel biosensors are comprised of platinum electrodes modified with composite films of (3-mercaptopropyl)trimethoxy silane xerogel embedded with glucose oxidase enzyme, doped with Au225(C6)75 MPCs, and coated with an outer polyurethane layer. Electrochemistry and scanning/transmission electron microscopy, including cross-sectional TEM, show sensor construction, humidity effects on xerogel structure, and successful incorporation of MPCs. Analytical performance of the biosensor scheme with and without MPC doping of the xerogel is determined from direct glucose injection during amperometry. MPC-doped xerogels yield significant enhancement of several sensor attributes compared to analogous films without nanoparticles: doubling of the linear range, sensitivity enhancement by an order of magnitude, and 4-fold faster response times accompany long-term stability and resistance to common interfering agents that are competitive with current glucose biosensing literature. Ligand chain length and the MPC/silane ratio studies suggest the MPC-induced enhancements are critically related to structure-function relationships, particularly those affecting interparticle electronic communication where the MPC network behaves as a three-dimensional extension of the working electrode into the xerogel film, reducing the system's dependence on diffusion and maximizing efficiency of the sensing mechanism. The integration of MPCs as a functional component of amperometric biosensor schemes has implications for future development of biosensors targeting clinically relevant species.