Advancing the analytical toolkit in the investigation of vector mosquito host biting site selection

High‐resolution mass spectrometry and ion mobility spectrometry provide additional confidence in biological marker discovery and elucidation by adding additional peak capacity through physiochemical separation orthogonal to chromatography. Sophisticated analytical techniques have proved valuable in the identification of human skin surface chemicals used by vector mosquitoes to find their human host. Polydimethylsiloxane (PDMS) was used as a non‐invasive passive wearable sampler to concentrate skin surface non‐volatile and semi‐volatile compounds prior to solvent desorption directly in an LC vial, thereby simplifying the link between extraction and analysis. Ultra‐performance liquid chromatography with ion mobility spectrometry coupled with high‐resolution mass spectrometry (UPLC‐IMS‐HRMS) was used for compound separation and detection. A comparison of the skin chemical profiles between the ankle and wrist skin surface region sampled over a 5‐day period for a human volunteer was done. Twenty‐three biomarkers were tentatively identified with the aid of a collision cross‐section (CCS) prediction tool, seven associated with the ankle skin surface region and 16 closely associated with the wrist skin surface. Ten amino acids were detected and unequivocally identified on the human skin surface for the first time. Furthermore, 22 previously unreported skin surface compounds were tentatively identified on the human skin surface using accurate mass, CCS values and fragmentation patterns. Method limits of detection for the passive skin sampling method ranged from 8.7 (sulfadimethoxine) to 95 ng (taurine). This approach enabled the detection and identification of as‐yet unknown human skin surface compounds and provided corresponding CCS values.