黑蒜是一種大蒜經過熱加工的產品，因其具有潛在的健康益處，故近年來人們對黑蒜的關注大幅提升，並將其應用在保健食品上。非標的代謝體學方法以生物系統中分子的全面表徵為研究重點，為研究黑蒜在熱過程中的化學變化提供了前景。本研究的主要目的是通過超高效液相層析-軌道阱高解析度質譜儀（UHPLC-Orbitrap HRMS）利用嫌疑清單掃描和非標的代謝體學方法來分析大蒜之代謝體，進而提供有關黑蒜熱加工的多面向探討。本研究分析了三批樣品，並且對三批樣本之訊號交集進一步進行了Student's t-test的統計分析，以p<0.001及倍數變化>10作為篩選基準挑選出具有顯著差異的訊號，並對這些訊號進行MS / MS分析。在50個鑑定到的結構中，含有8種有機硫化合物、33種有機酸、胺基酸及其衍生物，以及9種脂質和其衍生物。在加熱過程中，有機硫化物隨著時間減少，大多數的glycerophospholipids、shikimate、 aromatic amino acids及維生素B6等則呈現顯著增加而tryptophan隨時間減少並代謝形成nicotinate metabolism、 aminobenzoate degradation及Maillard reaction之相關代謝物；此外，可能具有致突變性的Heyns byproducts含量亦隨著時間增加。在此，我們利用了代謝體學方法，進行大蒜與黑蒜的比較分析並描繪黑蒜在加工過程中所發生的的化學成分變化，不僅為黑蒜生產提供了更加深入的剖析，亦為食品安全研究提供了相關見解。

In recent years, people have drawn their attention to black garlic, a kind of heat-treated product of garlic, and applied it to functional food because of the potential health benefits. An untargeted metabolomics approach, focusing on comprehensive characterizations of molecules in the biological system, has the potential to expand the horizons in the study of chemical changes in black garlic during the thermal process. The main objective of this study is to exploit suspect screening and untargeted approaches via ultrahigh-performance liquid chromatography-orbitrap high resolution mass spectrometry (UHPLC-Orbitrap HRMS) for profiling garlic metabolome to provide multi-aspect knowledge of the black garlic production. Three batches of samples were analyzed, and the overlapped region was further subjected to a statistical cutoff of Student's t-test p<0.001 and fold change>10. The features of significance were then selected for MS/MS analysis. A total of 50 probable structures, including 8 organosulfur compounds, 33 organic acids, amino acids and derivatives, and 9 lipids and derivatives were identified. Organosulfur compounds were decreased along with the heat process; instead, most of the glycerophospholipids together with shikimate, aromatic amino acids, and vitamin B6 vitamers were significantly augmented while tryptophan consumed to generate downstream products of nicotinate metabolism, aminobenzoate degradation, and Maillard reaction. Besides, Heyns byproducts that potentially produce mutagenic effects were concentrated. Herein, we introduced metabolomics approaches for the comparative analysis and portray chemical composition changes of black garlic processing. Our findings provide in-depth insights into the black garlic production as well as guidance for future biological and food safety research.

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