Magnetic mesoporous Fe3O4@nSiO2@mSiO2 nanoparticles for high-throughput mass spectrometry detection of hydrolyzed products of organophosphorus nerve agents.

Abstract

Rapid and accurate detection of hydrolyzed products of organophosphorus nerve agents (OPNAs) is an important method to effectively confirm the use of these agents. OPNAs are rapidly hydrolyzed to the methyl phosphonates (MPs) in the environment, which can be used as environmental traceability marker for OPNAs. Herein, magnetic mesoporous materials combined with real-time in situ mass spectrometry (MS) were used to achieve high-throughput detection of MPs. Novel magnetic mesoporous nanoparticles Fe3O4@nSiO2@mSiO2 were synthesized via co-condensation of tetraethyl orthosilicate and cetyltrimethylammonium bromide (CTAB) on the surface of nonporous silica-coated Fe3O4 under alkaline conditions. CTAB templates were removed by the reflux of ethanol (0.0375 mM ammonium nitrate) to form mesoporous SiO2, which has a large specific surface area of 549 m2 g-1 and an excellent magnetization strength of 59.6 emu g-1. A quick, cost-effective, rugged, and safe magnetic preparation method, magnetic QuEChERS, was established with magnetic mesoporous nanoparticles (Fe3O4@nSiO2@mSiO2) as adsorption materials for direct analysis in real-time and tandem MS (DART-MS/MS) of MPs in environmental samples. The method exhibits good linearity (R2 > 0.992) in the range of 20.0-4.00 μg mL-1, the limits of detection were <5.00 ng mL-1, the limits of quantification were <20.0 ng mL-1, and the extraction recoveries were 70.2-98.1%, with relative standard deviations (RSDs) in the range of 1.97-10.6%. Additionally, using this method, analysis of 70 environmental samples could be completed within 20 min. Then, the M-QuEChERS-DART-MS/MS method was applied to the 52nd Organisation for the Prohibition of Chemical Weapons (OPCW) environmental spiked samples analysis, where the accuracy was 95.2-116%, and the RSD was 1.16-7.83%. The results demonstrated that Fe3O4@nSiO2@mSiO2 based on the QuEChERS method can quickly and efficiently remove the matrix of environmental samples and when coupled with the DART-MS/MS can achieve high-throughput determination of MPs in environmental samples.