Herein, we propose a label-free chemiresistive sensor for the highly sensitive and selective detection of microcystin (MC)-LR in water samples. The sensor uses a layer-by-layer (LBL) assembled conductive film consisting of Ti3C2Tx nanosheets as the sensing channel. It is further modified by using an aptamer for the specific recognition of MC-LR. The response signal is based on the change in resistance of the conductive channel upon binding of MC-LR with the aptamer. Our novel strategy is the first concept proposed for immobilizing the aptamer containing -SH on the channel surface through a Ti-S bond under weakly alkaline condition. The resulting sensor is highly sensitive and stable for the detection of MC-LR, with a detection limit of 0.18 ng L-1 and a wide linear range from 1 to 104 ng L-1. We used the sensor to continuously monitor MC-LR released by cultivated Microcystis aeruginosa, showing a strong relationship between MC-LR and cell density. Furthermore, the sensor was successfully used to measure MC-LR in freshwater lakes with moderate algal blooms, and the results agreed well with those obtained by liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. The present study provides a reliable method for highly sensitive and selective detection of MC-LR in environmental waters.
Keywords: aptamer; chemiresistive sensor; label-free detection; microcystin-LR; self-assembled Ti3C2Tx film.