Online Charge-Generation Derivatization by Electrochemical Radical Cations of Thianthrene: Mass Spectrometry Imaging of Estrogens in Biological Tissues,Analytical Chemistry

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Online Charge-Generation Derivatization by Electrochemical Radical Cations of Thianthrene: Mass Spectrometry Imaging of Estrogens in Biological Tissues
Analytical Chemistry ( IF 6.7 ) Pub Date : 2024-07-20 , DOI: 10.1021/acs.analchem.4c02086
Yingchao Liu ₁ , Jiahui Bai ₁ , Xiaoxia Dong ₂ , Yuqi Cao ₁ , Mingmai Bao ₁ , Yingjie Lu ₃ , Hui Zeng ₄ , Lixing Zhan ₂ , Yinlong Guo ₁

Affiliation

Estrogens play a significant role in endocrinology and oncology. Although separation methods coupled with mass spectrometry (MS) have emerged as a powerful tool for studying estrogens, imaging the spatial distributions of estrogens is crucial but remains challenging due to its low endogenous concentration and poor ionization efficiency. Charge-generation derivatization, such as N-alkylpyridinium quaternization and S-methyl thioetherification, represents a method wherein neutral molecules involving analytes and derivatization reagents undergo chemical reactions to establish permanent charges directly onto the analytes to improve detection sensitivity. Here, we developed a novel derivatization reagent, thianthrene (TT), which enabled oxidization to radical cations ([TT]^•+) using an electrochemical method and completed the online charge-generation derivatization of estrogens on a mass spectrometry imaging platform. In this strategy, [TT]^•+ can efficiently and selectively derivatize estrogens via an electrophilic aromatic substitution reaction. Results indicated that derivatization with [TT]^•+ can significantly enhance imaging sensitivity (3 orders of magnitude), enabling the visualization of estrogen and its metabolites in ovarian and breast tissues. Furthermore, a higher mass intensity of these estrogens was captured in breast para-cancerous tissues than in cancerous tissues, which might provide estrogens spatial dimension information for further research on the initiation and progression of breast cancer.

中文翻译：

噻蒽电化学自由基阳离子在线电荷生成衍生化：生物组织中雌激素的质谱成像

雌激素在内分泌学和肿瘤学中发挥着重要作用。尽管分离方法与质谱 (MS) 相结合已成为研究雌激素的强大工具，但对雌激素的空间分布进行成像至关重要，但由于其内源浓度低和电离效率差，仍然具有挑战性。电荷产生衍生化，例如N-烷基吡啶季铵化和S-甲基硫醚化，代表了一种方法，其中涉及分析物和衍生试剂的中性分子进行化学反应，直接在分析物上建立永久电荷，以提高检测灵敏度。在这里，我们开发了一种新型衍生试剂噻蒽（TT），它可以利用电化学方法氧化为自由基阳离子（[TT] ^•+ ），并在质谱成像平台上完成雌激素的在线电荷发生衍生化。在该策略中，[TT] ^•+可以通过亲电芳香取代反应有效地、选择性地衍生化雌激素。结果表明，[TT] ^•+衍生化可以显着提高成像灵敏度（3 个数量级），从而实现卵巢和乳腺组织中雌激素及其代谢物的可视化。此外，在乳腺癌癌旁组织中捕获的这些雌激素的质量强度高于癌组织，这可能为进一步研究乳腺癌的发生和进展提供雌激素空间维度信息。

更新日期：2024-07-20

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