An efficient biosensor using a functionalized microneedle of Cu₂O-based CoCu-LDH for glucose detection

Glucose detection with small and micro volume sampling has recently received increasing attention in monitoring personal health. Herein, a cauliflower-type cluster of Cu₂O nanoparticles (NPs) was directly deposited on the tip surface of a stainless steel acupuncture needle electrode (ANE) by electrochemical deposition, and then this pre-formed cuprous basis was used to further prepare the neatly arranged CoCu-layered double hydroxide (CoCu-LDH) nanosheets that interconnected to form nano-sized pores in the range from 100 to 500 nm. The microstructure and spectral characteristics of the surface modification materials were comprehensively characterized by FE-SEM, EDS, XRD, FT-IR and TEM. Cu₂O-based CoCu-LDH composites with special morphology had been proven to accelerate the rate of electron transport and provide more available active centers, and moreover, the mixed valence of Cu/Co induced an excellent synergism for the electrocatalytic oxidation of glucose. As a result, CoCu-LDH/Cu₂O/ANE as a sensitive glucose probe exhibited two wider linear ranges of 0.03-0.40 mM and 0.40-6.00 mM, with sensitivities of 116.13 μA mM^-1 and 52.08 μA mM^-1, respectively, and the detection limit as low as 0.46 μM (S/N = 3). The response time only took 3 s and it kept working stably in the interference of ascorbic acid (AA), dopamine (DA), uric acid (UA), and Cl^-. In the stability test, the CoCu-LDH/Cu₂O/ANE sensor exhibited a stable monitoring sensitivity after 15 days. Finally, the CoCu-LDH/Cu₂O/ANE sensor had been successfully applied to glucose analysis in human serum, proving that our design was an attractive strategy for developing a portable, minimally invasive, and low-cost non-enzymatic electrochemical glucose sensing platform.