Department of Geoscience, University of Calgary, Calgary, Alberta, Canada.
Department of Anthropology and Archaeology, University of Calgary, Calgary, Alberta, Canada.
PLoS One. 2021 Nov 18;16(11):e0258779. doi: 10.1371/journal.pone.0258779. eCollection 2021.
This work introduces a novel analytical chemistry method potentially applicable to the study of archaeological starch residues. The investigation involved the laboratory synthesis of model Maillard reaction mixtures and their analysis through Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS). Thus, starch from sixteen plant species were matured while reacting it with the amino acid glycine. The FTICR-MS analysis revealed > 5,300 molecular compounds, with numerous unique heteroatom rich compound classes, ranging from 20 (Zea mays) to 50 (Sorghum bicolor). These classes were investigated as repositories of chemical structure retaining source and process-specific character, linked back to botanical provenance. We discussed the Maillard reaction products thus generated, a possible pathway for the preservation of degraded starch, while also assessing diagenetic recalcitrance and adsorption potential to mineral surfaces. In some cases, hydrothermal experimentation on starches without glycine reveals that the chemical complexity of the starch itself is sufficient to produce some Maillard reaction products. The article concludes that FTICR-MS offers a new analytical window to characterize starchy residue and its diagenetic products, and is able to recognize taxonomic signals with the potential to persist in fossil contexts.
这项工作介绍了一种新的分析化学方法，可能适用于考古淀粉残留物的研究。该研究涉及模型美拉德反应混合物的实验室合成及其通过傅里叶变换离子回旋共振质谱（FTICR-MS）进行分析。因此，将来自 16 种植物的淀粉与氨基酸甘氨酸反应使其成熟。FTICR-MS 分析揭示了>5300 种分子化合物，具有许多独特的富含杂原子的化合物类别，范围从 20（玉米）到 50（高粱）。这些类别被用作保留来源和过程特异性特征的化学结构库，与植物学起源相关联。我们讨论了由此产生的美拉德反应产物，这是一种保存降解淀粉的可能途径，同时还评估了对矿物表面的非成岩抗性和吸附潜力。在某些情况下，没有甘氨酸的淀粉的热液实验表明，淀粉本身的化学复杂性足以产生一些美拉德反应产物。本文得出的结论是，FTICR-MS 为表征淀粉残留物及其成岩产物提供了一个新的分析窗口，并且能够识别具有在化石背景中持续存在潜力的分类信号。
