Fornasaro Stefano, Gotts Nigel, Venturotti Gioia, Muelas Marina Wright, Roberts Ivayla, Sergo Valter, Goodacre Royston, Bonifacio Alois
Department of Chemical and Pharmaceutical Sciences, University of Trieste, via L. Giorgieri 1, 34127 Trieste, Italy.
Centre for Metabolomics Research, Department of Biochemistry, Cell and Systems Biology, Institute of Systems, Molecular, and Integrative Biology, University of Liverpool, Liverpool L69 7ZB, UK.
Analyst. 2025 Jan 27;150(3):559-566. doi: 10.1039/d4an01323a.
Ergothioneine (ERG) is a natural sulfur-containing amino acid found in many organisms, including humans. It accumulates at high concentrations in red blood cells and is distributed to various organs, including the brain. ERG has numerous health benefits and antioxidant capabilities, and it has been linked to various human physiological processes, such as anti-inflammatory, neuroprotective, and anti-aging effects. Accurate, rapid, and cost-effective quantification of ERG levels in human biofluids is crucial for understanding its role in oxidative stress-related diseases. Surface-enhanced Raman scattering (SERS) is an effective approach for measuring compounds at concentrations similar to those at which ERG is present in serum. However, while SERS has been used to characterize or detect ERG, quantification has not yet been achieved due to the variability in the signal enhancement that can arise during sample preparation and analysis. This study introduces a highly efficient and reliable technique for quickly (20 min is typical per sample) measuring ERG levels in human serum using SERS. This employs an internal standard highly specific for ERG which resulted in limit of quantification values of 0.71 μM. To validate this approach, we analysed real human serum with unknown ERG levels as a blind test set and primary reference levels of ERG were produced using a targeted UHPLC-MS/MS reference method.
麦角硫因（ERG）是一种天然含硫氨基酸，存在于包括人类在内的许多生物体中。它在红细胞中高浓度积累，并分布到包括大脑在内的各个器官。麦角硫因具有多种健康益处和抗氧化能力，并且与各种人类生理过程有关，如抗炎、神经保护和抗衰老作用。准确、快速且经济高效地定量测定人体生物流体中的麦角硫因水平对于了解其在氧化应激相关疾病中的作用至关重要。表面增强拉曼散射（SERS）是一种在与血清中麦角硫因相似的浓度下测量化合物的有效方法。然而，虽然SERS已用于表征或检测麦角硫因，但由于样品制备和分析过程中可能出现的信号增强变化，尚未实现定量。本研究介绍了一种高效可靠的技术，可使用SERS快速（每个样品通常20分钟）测量人血清中的麦角硫因水平。该技术采用了对麦角硫因具有高度特异性的内标，定量限为0.71 μM。为了验证该方法，我们将未知麦角硫因水平的真实人血清作为盲测集进行分析，并使用靶向超高效液相色谱-串联质谱参考方法得出麦角硫因的主要参考水平。
