Human skin surface chemical cues comprise a complex mixture of compounds that mosquitoes use to locate and select their human host, based on inter‐ and intra‐human variation in chemical profiles. The complexity of the skin surface matrix calls for advanced analytical techniques to enable separation and identification of biomarkers, which may be used as topical attractants and repellants in future mosquito vector control programmes. The perceived mosquito attractiveness between 20 volunteers and the preference of mosquitoes to bite certain regions, namely, ankle versus wrist, of the human host were investigated in this study, by comparing skin surface chemical profiles. Ion mobility was combined with high resolution mass spectrometry to provide additional confidence in biological marker discovery and identification of human skin surface compounds. This study employed a non‐intrusive sampling scheme using a polydimethylsiloxane (PDMS) sampler and solvent desorption analysed with ultra‐performance liquid chromatography with ion mobility high‐resolution mass spectrometry (UPLC‐IMS‐HRMS). Statistical approaches guided the identification of 14 biological markers discerning difference in perceived mosquito attractiveness and 20 biomarkers associated with the different skin regions sampled. A broad range (m/z 96.0437 to 788.6095) of chemical compounds was detected from a variety of classes (including sugars, steroids, fatty acids, peptides and peptide derivatives, and compounds of food origin). Ten compounds were unequivocally identified on the human skin surface, and caffeine was reported on the human skin surface for the first time. Furthermore, 77 compounds, of which 64 to the authors' knowledge have not previously been reported, were detected on the human skin surface using accurate mass, collision cross section (CCS) values and fragmentation patterns. This approach enabled comprehensive human skin surface chemical profiling and provides an extensive list of tentatively identified skin surface compounds together with accurate mass values and adducts with their corresponding CCS values.

中文翻译：

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用于蚊媒控制应用的人体皮肤表面的质谱研究

人类皮肤表面化学线索包括复杂的化合物混合物，蚊子根据化学特征的人际和人内变化，用来定位和选择人类宿主。皮肤表面基质的复杂性需要先进的分析技术来分离和识别生物标志物，这些生物标志物可在未来的蚊媒控制计划中用作局部引诱剂和驱避剂。在这项研究中，通过比较皮肤表面化学特征，研究了 20 名志愿者之间感知到的蚊子吸引力以及蚊子对某些区域（即脚踝与手腕）叮咬的偏好。离子淌度与高分辨率质谱相结合，为生物标志物的发现和人体皮肤表面化合物的鉴定提供了额外的信心。本研究采用非侵入式采样方案，使用聚二甲基硅氧烷 (PDMS) 进样器和溶剂解吸，并使用具有离子迁移率高分辨率质谱的超高效液相色谱 (UPLC-IMS-HRMS) 进行分析。统计方法指导识别 14 种生物标记物，这些标记物可识别蚊子吸引力的差异，以及与采样的不同皮肤区域相关的 20 种生物标记物。一个大范围 （统计方法指导识别 14 种生物标记物，这些标记物可识别蚊子吸引力的差异，以及与采样的不同皮肤区域相关的 20 种生物标记物。一个大范围 （统计方法指导识别 14 种生物标记物，这些标记物可识别蚊子吸引力的差异，以及与采样的不同皮肤区域相关的 20 种生物标记物。一个大范围 （m/z 96.0437 至 788.6095) 的化合物来自各种类别（包括糖类、类固醇、脂肪酸、肽和肽衍生物以及食品来源的化合物）。十种化合物在人体皮肤表面被明确鉴定，咖啡因首次在人体皮肤表面被报道。此外，使用精确质量、碰撞横截面 (CCS) 值和碎裂模式在人体皮肤表面检测到 77 种化合物，其中 64 种据作者所知以前没有报道过。这种方法实现了全面的人体皮肤表面化学分析，并提供了广泛的初步确定的皮肤表面化合物列表，以及准确的质量值和加合物及其相应的 CCS 值。