Photocatalytically renewable peptide-based electrochemical impedance method for sensing lipopolysaccharide

A peptide (Li5-025)-modified gold nanoparticle (AuNP)/(titania (TiO₂) + 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphine (TAPP))/glassy carbon electrode (GCE) was developed for lipopolysaccharide (LPS) determination. This electrode not only performs well in the electrochemical impedance determination of LPS in serum but can also be easily regenerated under light irradiation. Using Fe(CN)₆^3-/4- as a redox probe, LPS recognition can be indicated by the significantly increased electron-transfer resistance (R_et) as a result of the coaction of the increased steric hindrance from the peptide-LPS complex and the electrostatic repulsion between LPS and Fe(CN)₆^3-/4-. The impedimetric signal was acquired in the frequency range 0.1 Hz ~ 100 kHz with an initial voltage of 174 mV and an amplitude of 10 mV. The resistance changes (ΔR_et) are linearly related to the LPS concentrations in a broad range (0.1 pg mL^-1 ~ 100 ng mL^-1) with a low detection limit (0.08 pg mL^-1). Importantly, the electrode shows high selectivity to LPS from Escherichia coli O55:B5 compared to other bacterial sources and considerable anti-interference to 0.1% fetal calf serum, demonstrating its potential application in clinically relevant samples. Another highlight is that the AuNP/(TiO₂ + TAPP)/GCE surface can be photocatalytically regenerated under light irradiation (50 mW cm^-2, 300-2500 nm) without any obvious damage to the electrode microstructure. After simple peptide re-immobilization, the regenerated electrode demonstrates LPS response similar to the peptide less one, and the deviation is only 2.89% after 5-cycle reuse. Graphical abstract A peptide (Li5-025)-modified AuNP/(TiO₂ + TAPP porphine)/GCE was proposed, which not only has excellent electrochemical analytical performances for LPS assay in serum but also can be reused after light irradiation and subsequent peptide re-immobilization.