A novel route for identifying starch diagenetic products in the archaeological record

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 Spectromet...

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Bibliographic Details
Published in:	PloS one 2021-11, Vol.16 (11), p.e0258779-e0258779
Main Authors:	Oldenburg, Thomas, Brown, Melisa, Inwood, Jamie, Radović, Jagoš, Snowdon, Ryan, Larter, Steve, Mercader, Julio
Format:	Article
Language:	eng
Subjects:	Amino acids Analytical chemistry Archaeology Archaeology - methods Biology and Life Sciences Carbohydrates Chemical synthesis Chemistry Chemistry Techniques, Analytical Cyclotron resonance Cyclotrons Earth science Evaluation Experimentation Fourier transforms Funding Glycine Humans Ions Maillard Reaction Maillard reaction products Mass spectrometry Mass spectroscopy Molecular weight Physical Sciences Plant species Polymers Product introduction Properties Reaction products Research and Analysis Methods Residues Scientific imaging Social Sciences Sorghum Sorghum - chemistry Spectroscopy, Fourier Transform Infrared Starch Starch - chemistry Starch - isolation & purification Starches Supervision Zea mays - chemistry
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Summary:	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.
ISSN:	1932-6203 1932-6203