High-throughput screening and spatial profiling of low-mass pesticides using a novel Ti3C2 MXene nanowire (TMN) as MALDI MS matrix

Abstract

Pesticides play critical roles in agricultural fields; however, pesticide residues can cause serious damage to human health and the ecological environment; therefore, developing a rapid and sensitive method for pesticide detection is urgently needed. Nanostructure-assisted matrix laser desorption/ionization (MALDI) mass spectrometry (MS) has great potential for the detection of low-mass pesticides. In this study, a novel Ti₃C₂ MXene nanowire (TMN) was prepared by a facile sol-gel method and served as a matrix to enhance MALDI MS performance in the analysis of pesticides in positive ion mode. The TMN showed superior performance in the high-throughput detection of six kinds of pesticides (organophosphorus, organochlorine, carbamate, neonicotinoids, triazole, and oxadiazines), with ultrahigh sensitivity (detection limits at sub-ppt levels), remarkable repeatability, excellent salt tolerance, and extremely low background compared to traditional organic matrices due to the specific polyaromatic structure and the doping of nitrogen. Furthermore, this matrix was successfully employed for the analysis of residual pesticides in traditional Chinese herbs, and the level of diniconazole was quantified with a linear range of 0-50 ng/mL (R² > 0.99). More importantly, the spatial distribution of various endogenous compounds (e.g., amino acids and saccharides, fatty acids, alkaloids, and plant hormones) and xenobiotic pesticides from the intact root of the medicinal plant P. quinquefolium was clearly visualized using the TMN self-assembly film as a matrix for MALDI imaging mass spectrometry (IMS). With superior advantages such as sensitivity, simplicity, rapidness, and minimal sample requirement, TMN as a matrix-assisted MALDI MS shows great promise for various applications.

Keywords: MALDI MS; Mass spectrometry imaging; Pesticides; TMN; Traditional Chinese herbs.