Electrochemical Oxidation of Monosaccharides at Nanoporous Gold with Controlled Atomic Surface Orientation and Non-Enzymatic Galactose Sensing

Abstract

Non-enzymatic saccharide sensors are of great interest in diagnostics, but their non-selectivity limits their practical diagnostic abilities. In this study, we investigated the electrochemical oxidation of monosaccharides at nanoporous gold (NPG) catalysts with different contributions of surface crystallographic orientations. Fructose elicited no clear electrochemical response, but glucose, galactose, and mannose produced clear oxidative current. The onset potentials for oxidation of these saccharides depended on the surface atomic structure of the NPG. The oxidation potential was approximately 100 mV less positive at the Au(100)-enhanced NPG than at the Au(111)-enhanced NPG. Furthermore, the voltammetric responses significantly differed among the saccharides. Galactose was oxidized at less positive potential and exhibited a higher current response than the other saccharides. This tendency was enhanced in the presence of chloride ions. These features enabled the selective and sensitive detection of galactose at an NPG electrode without enzymes under physiological conditions. A linear range of 10 μM to 1.8 mM was obtained in the calibration plot, which was comparable to those in previously reported enzymatic galactose sensors. Thus, we demonstrated that controlling the crystallographic orientation on the nanostructured electrode surface is useful in developing electrochemical sensors.