Abstract The aim of this study was to characterise the microbial and metabolite diversity in samples of biodeteriorated 18th century silk from the burial crypts of the Church of St Francis of Assisi in Krakow (Poland). Highthroughput Illumina sequencing, surface-assisted laser desorption/ionisation mass spectrometry on a silver nanoparticle enhanced target (109Ag SALDI), and laser ablation-remote-electrospray ionisation-selected reaction monitoring-ambient mass spectrometry imaging (LARESI MSI) were employed. The use of high throughput Illumina sequencing helped obtain a broader picture of microbiocenosis compared to earlier studies. The 109Ag SALDI method enabled the qualitative analysis of the entire chemical compound profile of silk. A few hundred metabolites, including peptides, amino acids, urea and organic acids dominated by N-(3-oxododecanoyl)-L-homoserine, decanoylcholine, formiminoalanine and hexacosatrienoic acid were detected in archaeological silk, whereas about 100 metabolites, mainly represented by polymers, were detected in contemporary and restored silk. The novel ambient MS imaging method LARESI MSI, used for the first time for the archaeological silk biodeterioration analysis, allowed the direct detection and mapping of selected amino acids, historical dyes and dihydroxybenzoic acid (decomposition product of tannins) on the silk samples. Based on our results, the suitability of the tested methods should also be considered for other historical objects.

中文翻译：

---

18世纪考古丝绸的代谢组学和宏基因组学分析

摘要 本研究的目的是表征来自克拉科夫（波兰）阿西西圣弗朗西斯教堂墓穴的 18 世纪生物腐烂丝绸样品中微生物和代谢物的多样性。采用高通量 Illumina 测序、银纳米粒子增强靶标 (109Ag SALDI) 上的表面辅助激光解吸/电离质谱法和激光烧蚀-远程-电喷雾电离-选择反应监测-环境质谱成像 (LARESI MSI)。与早期研究相比，使用高通量 Illumina 测序有助于更广泛地了解微生物群落。109Ag SALDI 方法能够对丝绸的整个化学成分进行定性分析。数百种代谢物，包括肽、氨基酸、在考古丝绸中检测到尿素和以 N-(3-氧代十二烷酰基)-L-高丝氨酸、癸酰胆碱、甲亚氨基丙氨酸和六十二碳三烯酸为主的有机酸，而在当代和修复的丝绸中检测到大约 100 种代谢物，主要以聚合物为代表。新的环境 MS 成像方法 LARESI MSI 首次用于考古丝绸生物退化分析，可以直接检测和映射丝绸样品上的选定氨基酸、历史染料和二羟基苯甲酸（单宁的分解产物）。根据我们的结果，还应考虑测试方法对其他历史对象的适用性。主要以聚合物为代表，在当代和修复的丝绸中被检测到。新的环境 MS 成像方法 LARESI MSI 首次用于考古丝绸生物退化分析，可以直接检测和绘制丝绸样品上的选定氨基酸、历史染料和二羟基苯甲酸（单宁的分解产物）。根据我们的结果，还应考虑测试方法对其他历史对象的适用性。主要以聚合物为代表，在当代和修复的丝绸中被检测到。新的环境 MS 成像方法 LARESI MSI 首次用于考古丝绸生物退化分析，可以直接检测和映射丝绸样品上的选定氨基酸、历史染料和二羟基苯甲酸（单宁的分解产物）。根据我们的结果，还应考虑测试方法对其他历史对象的适用性。