Electrochemical Glucose Sensors Enhanced by Methyl Viologen and Vertically Aligned Carbon Nanotube Channels

Freestanding, vertically aligned carbon nanotubes (VACNTs) were patterned into 16 μm diameter microchannel arrays for flow-through electrochemical glucose sensing. Non-enzymatic sensing of glucose was achieved by the chemical reaction of glucose with methyl viologen (MV) at an elevated temperature and pH (0.1 M NaOH), followed by the electrochemical reaction of reduced-MV with the VACNT surface. The MV sensor required no functionalization (including no metal) and was able to produce on average 3.4 electrons per glucose molecule. The current density of the MV sensor was linear with both flow rate and glucose concentration. Challenges with interference chemicals were mitigated by operating at a low potential of -0.2 V vs Ag/AgCl. As a comparison, enzymatic VACNT sensors with platinum nano-urchins were functionalized with glucose oxidase by covalent binding (1-ethyl-3-(-3-dimethylaminopropyl)carbodiimide/ N-hydroxysuccinimide) or by polymer entrapment [poly(3,4-ethylene-dioxythiophene)] and operated in phosphate buffered saline. With normalization by the overall cross-sectional area of the flow (0.713 cm²), the sensitivity of the MV, enzyme-in-solution, and covalent sensors were 45.93, 18.77, and 1.815 mA cm^-2 mM^-1, respectively. Corresponding limits of detection were 100, 194, and 311 nM glucose. The linear sensing ranges for the sensors were 250 nM to 200 μM glucose for the MV sensor, 500 nM to 200 μM glucose for the enzyme-in-solution sensor, and 1 μM to 6 mM glucose for the covalent sensor. The flow cell and sensor cross-sectional area were scaled down (0.020 cm²) to enable detection from 200 μL of glucose with MV by flow injection analysis. The sensitivity of the small MV sensor was 5.002 mA cm^-2 mM^-1, with a limit of detection of 360 nM glucose and a linear range up to at least 150 μM glucose. The small MV sensor has the potential to measure glucose levels found in 200 μL of saliva.