RuSe2/CuO nanohybrids coupled with ALP-assisted for MMP-9 photoelectrochemical assay

Abstract

A photoelectrochemical (PEC) assay strategy for the detection of matrix metalloproteinase-9 (MMP-9) was fabricated. RuSe2/CuO nanohybrids were first prepared by hydrothermal method. As a transition metal element semiconductor, RuSe2 has excellent optical and electrical properties. By combining the excellent conductivity and adjustable bandgap of CuO, a binary heterojunction nanoflower with high photoelectric response was obtained. The combination of RuSe2 and CuO reduces the electron hole recombination rate; the RuSe2/CuO nanohybrids exhibits a higher photocurrent response. In the MMP-9 PEC strategy determination, the magnetic beads (MB)-peptide-alkaline phosphatase (ALP) recognition probe was formed by modifying C-terminal of the peptide chain with biotin and binding to ALP, and the N-terminal was connected to carboxylated MB. When the target MMP-9 exists, the recognition probe, MB-Peptide-ALP, was recognized by MMP-9 to cut the substrate area and coding area and release ALP, catalyzing the hydrolysis of O-phosphonoxyphenol (OPP) to produce benzene-1,2-diol in situ, the photocurrent response was generated. This strategy provides lower background PEC noise for detecting MMP-9, with the advantage of simplicity and the sensitivity than conventional ELISA. The results showed that the recognition peptide probe PEC method achieved ultra-high sensitivity detection of target MMP-9, with a linear detection range of 1 pg/mL–100 ng/mL and a detection limit of 0.3 pg/mL (S/N = 3). The results of PEC assay strategy in human serum sample give the recoveries rate of 94.3 % to 108.1 % and relative standard deviation of 0.45–5.87 %.