In this study, the composite material that made up polyglycine/3d-4f hybrid-metallic cyano-bridged mixed coordination polymers (CyMCP) was successfully decorated onto a glassy carbon rotating disk electrode (GC RDE) using electrodeposition. The voltammetric behavior of NADH showed typical direct electrooxidation characteristics on the modified GC electrode. Our polyglycine/CyMCP-modified GC RDE was able to measure the apparent heterogeneous electron transfer rate constant of NADH during its direct electrooxidation by preventing fouling effects on the working electrode, which would generally cause a decrease in the oxidative peak current of NADH. In addition, differential pulse voltammetry provided a large linear range between the oxidative peak current and the concentration of NADH from 2-1500 μM at the polyglycine/CyMCP/GC electrode. Finally, the apparent heterogeneous electron transfer rate constant (k s NADH ) of NADH was determined to be 1.73 × 10 −2 cm · s −1 using the polyglycine/CyMCP-modified GC RDE. Both reduced and oxidized forms of β-nicotinamide adenine dinucleotide (NADH and NAD + , respectively) are the coenzymes for a large number of dehydrogenase enzymes (>300) and components of biomarker systems.1 In fact, because of its very important role in the field of analytical electrochemistry, 2,3 bioelectrocatalysis 4-6 and biofuel cells, 7,8 the electrochemical investigation for the formal potential of NADH/NAD + redox couple has attracted much attention.
9,10Therefore, direct oxidation of NADH at untreated or unmodified classical solid electrodes is known to appear poor reversibility and occurs with considerable overpotential (e.g., 1.1 V on carbon and 1.3 V on platinum). [11][12][13][14][15][16] Furthermore, accumulation of oxidation products involving radical intermediates, such as dimer from the one-electron oxidation product NAD +. , 17,18 can cause deactivation and fouling of the electrode surface. Such contamination of the working electrode can largely lower the sensitivity and reproducibility of voltammetric measurements. Consequently, considerable effort has been devoted with a strategy of surface modification on the substrate of conventional materials electrode to attain the electrode's long term stability for determination of NADH at a lower potential. 2,[19][20][21] Over the last few decades, various carbon nanomaterial 22-24 and redox-active mediator materials [25][26][27][28][29][30][31][32][33][34][35] have been modified onto the electrode surface in order to alleviate and/or prevent higher overpotential and fouling problems of the electrode. Therefore, there exist two kinds of catalytic model for the electrooxidation of NADH: one is a direct electro-catalysis 13,15,16,36 and the other is called a redox mediator electro-catalysis. [25][26][27][28][29][30][31][32]37 Though these redox mediators are very efficient electron shuttles for NADH oxidation processes, hydrodynamic voltammetry on the mediator-modified electrode remains a challenge for examining the kinetic parameters of NADH elect...