Wearable Solid-Phase Microextraction Sampling for Enhanced Detection of Volatile Analytes in Human Ears

Investigating ear at molecule level is challenging task, since there is a lack of molecular detection by traditional diagnosis techniques such as otologic endoscopy, ear swab culture, and imaging diagnostic technique. Therefore, new development of noninvasive, highly sensitive, and convenient analytical method for investigating human ears is highly needed. We developed a wearable sampling device for extracting trace analytes in ear by fixing solid-phase microextraction fibers into modified earmuffs (SPME-in-earmuffs). After sampling, SPME fiber was coupled with gas chromatography-mass spectrometry (GC-MS) for identification and quantification of extracted analytes. Enhanced detection of various analytes such as volatile metabolites, exposures, and therapeutic drugs of ears were demonstrated in this work. Particularly, sport-induced metabolic changes such as fatty acids, aldehyde compounds and oxidative produces were found from human ears using this method. Acceptable analytical performances were obtained by using this newly developed method for detecting ear medicines, e.g., low limit of detection (LOD, 0.005-0.021 ng/mL) and limit of quantification (LOQ, 0.018-0.071 ng/mL), excellent linear dynamic responses (R2 > 0.99, ranging from 0.50 ∼ 8.00 ng/mL), good relative standard deviations (RSDs, 13.19 % ∼ 21.40 %, n = 6) and accuracy (84.43-150.18 %, n = 6) at different concentrations. For the first time, this work provides a simple, convenient, and wearable microextraction method for enhanced detection of trace volatiles in human ears. The enclosed space between ear and earmuff allows headspace SPME sampling of volatile analytes, and thus provides a new wearable method for monitoring ear metabolites and human exposures, showing potential applications in human health, disease diagnosis, and sport science.