Development of desorption electrospray mass spectrometry (DESI-MS) for analysis of ancient lipids from food residues on archaeological artefacts

开发解吸电喷雾质谱 (DESI-MS)，用于分析考古文物上食物残渣中的古代脂质

• 批准号: NE/I01959X/1
• 负责人: Jane Thomas-Oates
• 金额: $ 8.96万
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Training Grant
• 财政年份: 2011
• 资助国家: 英国
• 起止时间: 2011 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=NE%2FI01959X%2F1
• 关键词: Development; desorption; electrospray; mass; spectrometry

The extraction and mass spectrometric analysis of lipids from archaeological artefacts to gain information regarding the artefact is well established and beginning to be used to tackle high profile archaeological questions of international significance. To realise their full potential, such methods need to be applied to large numbers of artefacts (e.g. ceramic vessels) from a wide range of contexts and sites. However, LC- or derivatisation/GC-MS analyses of these extracts are time consuming and, since generally less than half of such extracts contain detectable lipid levels, often frustrating and wasteful. Consequently, a rapid, convenient, medium throughput approach to screening such extracts and obtaining structural information on their components would greatly facilitate analysis and allow prioritisation of samples for subsequent LC- or GC-MS analysis. DESI enables desorption and MS of analytes under ambient conditions directly from almost any surface. It is simple, sensitive, very rapid, and compatible with MS/MS approaches. We have recognised the potential of DESI-MS for archaeological applications, built a DESI source for our mass spectrometers, and shown its feasibility for lipid analysis from surfaces of typical archaeological materials. Although DESI analysis directly from artefact surfaces is appealing, it is rare that artefacts can be removed from museum collections to the MS lab for analysis. However, removal by experts of small samples of the surface of the ceramic, for extraction and GC- or LC- MS analysis is accepted. Preliminary data show successful direct DESI-MS/MS analysis of very small aliquots of such lipid extracts of archaeological ceramics, dried onto glass or into plastic 60-well plates, as well as DESI-FT-ICR-MS analysis of fatty acids in such extracts. This studentship will thus exploit the state-of-the-art mass spectrometers available in the high technology analytical facility, the York Centre of Excellence in Mass Spectrometry (CoEMS), to develop DESI-MS/MS for the rapid screening and first stage analysis of lipid extracts of archaeological artefacts. The student will optimise DESI-MS/MS for triacylgycerides, fatty acids and sterols in extracts desorbed from glass slides or multi-well plates, using medium and high resolution mass spectrometers, and determine limits of detection. We have archived over 500 lipid extracts from a wide range of ethnographic, historical and archaeological artefacts from different environments, and high temperature-GC and GC-MS data from all samples. The student will access this archive to optimise the approach, and test limits of detection. DESI-MS/MS will then be tested on selected extracts of the several hundred ceramic vessels from the Stonehenge World Heritage Site. Screening these extracts to identify samples for subsequent analysis by GC- and LC-MS will offer a massive saving in resources and investigator time, enabling deeper sampling and thus inference. Application to this high profile site will also 'showcase' the method and expose the student to the wider archaeological community and the media. The CoEMS provides a unique focus for a coherent and innovative programme of training for our PhD students in areas directly relevant to the NERC-RSC initiative, providing graduate level courses tailored specifically to the needs of PhD students working with high technology instrumentation. In addition to the outstanding networking and training opportunities of CoEMS, the student will belong to the Analytical Science and Environmental Chemistry research group, and gain enviable and unusual multidisciplinary training via membership of BioArCh, a joint venture of Archaeology, Biology and Chemistry at York. Our project partners are pioneers in the analysis of lipids from artefacts using established LC- and GC-MS approaches, and also represent the museum user community, further extending the unique training offered by this project.

从考古文物中脂质的提取和质谱分析已建立了有关人工制品的信息，并开始用于解决具有国际意义的备受瞩目的考古问题。为了实现其全部潜力，需要将这些方法应用于各种环境和地点的大量人工制品（例如陶瓷容器）。但是，这些提取物的LC或衍生化/GC-MS分析很耗时，由于通常不到此类提取物的一半含有可检测的脂质水平，通常令人沮丧和浪费。因此，一种快速，方便，中等吞吐量的方法来筛选此类提取物并在其组件上获得结构信息，将极大地促进分析并允许样品的优先级，以进行随后的LC-或GC-MS分析。 DESI在几乎任何表面都可以在环境条件下对分析物的解吸和MS。它简单，敏感，非常快，并且与MS/MS方法兼容。我们已经认识到DESI-MS在考古应用中的潜力，为我们的质谱仪建立了DESI来源，并显示了其从典型考古材料表面的脂质分析的可行性。尽管直接从人工体表面进行的DESI分析很有吸引力，但很少可以将人工制品从博物馆收藏中删除到MS Lab进行分析。但是，专家的少量样品的去除陶瓷表面，用于提取和GC-或LC- MS分析。初步数据显示，这种考古陶瓷的脂质提取物非常小的等分试样成功地直接DESI-MS/MS分析，干燥到玻璃上或塑料60孔板中，以及此类提取物中脂肪酸的DESI-FT-ICR-MS分析。因此，该学生将利用高科技分析设施，约克质谱卓越中心（COEMS）的最先进的质谱仪（COEMS），以开发DESI-MS/MS，以快速筛选和对考古文物的脂质提取物进行快速筛查和第一阶段分析。学生将使用中和高分辨率的质谱仪优化DESI-MS/MS，用于从载玻片或多电池板上解吸的提取物中的脂肪酸和固醇，并确定检测的限制。我们已经从不同环境中的广泛的人种学，历史和考古伪像以及所有样品中的高温GC和GC-MS数据存档了500多种脂质提取物。学生将访问此存档以优化方法，并测试检测限制。然后，将对来自巨石阵世界遗产的几百个陶瓷船的选定提取物进行测试。筛选这些提取物以识别样品以通过GC-和LC-MS进行后续分析，将为资源和研究者时间提供大量节省，从而可以更深入地采样并因此推理。在此备受瞩目的网站上的应用还将“展示”该方法，并将学生暴露于更广泛的考古界和媒体。 COEMS为与NERC-RSC计划直接相关的领域的博士学生提供了连贯和创新的培训计划，为研究生级课程提供了专门针对使用高科技仪器工作的博士学位学生的需求而进行的独特重点。除了COEM的出色网络和培训机会外，该学生还将属于分析科学和环境化学研究小组，并通过Bioarch的成员身份获得令人羡慕和不寻常的多学科培训，这是约克考古，生物学和化学合资企业。我们的项目合作伙伴是使用已建立的LC-和GC-MS方法对脂质分析的脂质的先驱，也代表博物馆用户社区，进一步扩展了该项目提供的独特培训。