Metabolomics analysis of biological samples is widely applied in medical and natural sciences. Assigning the correct chemical structure in the metabolite identification process is required to draw the correct biological conclusions and still remains a major challenge in this research field. Several metabolite tandem mass spectrometry (MS/MS) fragmentation spectra libraries have been developed that are either based on computational methods or authentic libraries. These libraries are limited due to the high number of structurally diverse metabolites, low commercial availability of these compounds, and the increasing number of newly discovered metabolites. Phase II modification of xenobiotics is a compound class that is underrepresented in these databases despite their importance in diet, drug, or microbiome metabolism. The O-sulfated metabolites have been described as a signature for the co-metabolism of bacteria and their human host. Herein, we have developed a straightforward chemical synthesis method for rapid preparation of sulfated metabolite standards to obtain mass spectrometric fragmentation pattern and retention time information. We report the preparation of 38 O-sulfated alcohols and phenols for the determination of their MS/MS fragmentation pattern and chromatographic properties. Many of these metabolites are regioisomers that cannot be distinguished solely by their fragmentation pattern. We demonstrate that the versatility of this method is comparable to standard chemical synthesis. This comprehensive metabolite library can be applied for co-injection experiments to validate metabolites in different human sample types to explore microbiota-host co-metabolism, xenobiotic, and diet metabolism.

中文翻译：

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快速制备大型硫酸盐代谢物文库用于人体样品的结构验证

生物样品的代谢组学分析已广泛应用于医学和自然科学中。在代谢物鉴定过程中分配正确的化学结构是得出正确的生物学结论所必需的，仍然是该研究领域的主要挑战。已经开发了一些基于计算方法或真实库的代谢物串联质谱（MS / MS）碎片谱库。这些文库受到限制，原因是结构上多样化的代谢物数量众多，这些化合物的商业可得性低以及新发现的代谢物数量不断增加。异种生物的II期修饰是一个化合物类别，尽管它们在饮食，药物或微生物组代谢中很重要，但在这些数据库中代表性不足。该Ø硫酸盐代谢物已被描述为细菌及其人类宿主共代谢的标志。在这里，我们已经开发出一种简单的化学合成方法，用于快速制备硫酸盐代谢物标准品，以获得质谱碎裂模式和保留时间信息。我们报告准备38 O-硫酸化的醇和酚，用于测定其MS / MS裂解模式和色谱特性。这些代谢物中有许多是区域异构体，不能仅通过其片段化模式加以区分。我们证明该方法的多功能性可与标准化学合成相媲美。该综合代谢物库可用于共注射实验，以验证不同人类样品类型中的代谢物，以探索微生物群与宿主的新陈代谢，异种生物和饮食代谢。