Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Analyst. 2018 Oct 22;143(21):5127-5136. doi: 10.1039/c8an01040d.
A method has been developed for extracting poppy alkaloids from oily matrices, specifically lipid residues associated with archaeological ceramics. The protocol has been applied to fresh and artificially aged poppyseed oil and to residue from a Late Bronze Age Cypriot juglet in the collections of the British Museum. The juglet is of a type that has been linked with ancient trade in opium due to its poppy-head shape and wide distribution; it is a rare example of an intact vessel with contents sealed inside. Bulk analysis of the residue by GC-EI-MS and pyGC-EI-MS indicated a degraded plant oil and possible presence of papaverine. Analysis of the alkaloid extracts by HPLC-ESI-MS using both triple quadrupole and FTICR mass spectrometers detected the five primary opium alkaloids in fresh poppyseed oil and papaverine in most of the aged samples. Papaverine and thebaine were detected in the juglet residue, providing the first rigorous chemical evidence to support a link between this vessel type and opium, or at least poppies. The association of opium with oil raises new questions about the ancient purpose of the commodities within these vessels, and the low levels (ng g-1) of opiates detected in this unusually well-preserved residue shed doubt on the scope for their detection in more fragmentary ceramic remains (potsherds). Papaverine was found to exhibit challenging carryover behaviour in all the analytical methods used in this study. The phenomenon has not been reported before and should be considered in future analyses of this analyte in all application areas.
已经开发出一种从油性基质中提取罂粟生物碱的方法,特别是与考古陶瓷相关的脂质残留物。该方案已应用于新鲜和人工老化的罂粟籽油以及大英博物馆收藏的一件 Late Bronze Age Cypriot juglet 的残留物。该 juglet 是一种由于其罂粟头形状和广泛分布而与古代鸦片贸易有关的类型;它是一种罕见的完整容器内密封内容物的例子。通过 GC-EI-MS 和 pyGC-EI-MS 对残留物进行的批量分析表明,存在降解的植物油和可能存在的罂粟碱。使用三重四极杆和 FTICR 质谱仪对生物碱提取物进行 HPLC-ESI-MS 分析,在新鲜罂粟籽油和大多数老化样品中检测到五种主要的鸦片生物碱和罂粟碱。在 juglet 残留物中检测到罂粟碱和可待因,为这种容器类型与鸦片或至少与罂粟之间的联系提供了第一个严格的化学证据。鸦片与油的关联提出了关于这些容器内商品的古代用途的新问题,而且在这种异常保存完好的残留物中检测到的阿片类药物水平很低(ng g-1),这对在更零碎的陶瓷残留物(陶器碎片)中检测它们的范围提出了质疑。在本研究中使用的所有分析方法中都发现罂粟碱表现出具有挑战性的残留行为。这种现象以前没有报道过,应该在未来所有应用领域对该分析物的分析中加以考虑。