应用热裂解气相色谱质谱技术对六种蛋白质类胶结材料的分析与鉴别
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(1.北京科技大学科技史与文化遗产研究院,北京 100083;2.中国文化遗产研究院,北京 100029;3.河南省文物建筑保护研究院,河南郑州 450002)

作者简介:

付迎春(1993—),女,北京科技大学科学技术史专业博士研究生,研究方向为文物中有机质材料研究,E-mail: bullet_1@163.com 通信作者:魏书亚,北京科技大学教授,研究方向为文物及文物保护中的有机质材料研究,E-mail: sywei66@hotmail.com

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国家重点研发计划重点专项项目(2020YFC1522402)资助


Identification and classification of six kinds of proteinaceous binding media by THM-Py-GC/MS
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(1. Institute of Cultural Heritage and History of Science & Technology, University of Science and Technology Beijing, Beijing 100083, China;2. Chinese Academy of Cultural Heritage, Beijing 100029, China;3. Henan Provincial Institute of Cultural Relic Architecture Protection, Zhengzhou 450002, China)

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    摘要:

    利用在线甲基化水解-裂解气相色谱质谱(THM-Py-GC/MS)技术对古代壁画、彩绘等文物中常用的骨胶、皮胶、鱼鳔胶、蛋清、蛋黄和猪血等六种蛋白质类胶结材料进行分析,采用盖蒂保护研究所开发的RAdICAL系统对谱图进行解析,总结了每类材料的特征裂解产物。研究表明,吡咯类化合物,特别是吡咯、二吡咯二酮和哌嗪二酮类化合物可以作为骨胶和皮胶的识别组分,鱼鳔胶的识别组分除了上述吡咯类化合物之外,还包括胆固醇类化合物。吲哚类、血/蛋清标记物、磷酸三甲酯、脯氨酸类化合物是蛋清的识别组分。除了含有蛋清的4种识别成分之外,猪血的识别成分还包括胆固醇类化合物。蛋黄的识别组分是磷酸三甲酯、蛋黄标记物和胆固醇类化合物。最后利用主成分分析法(PCA)对福建省泉州市安海县龙山寺千手观音佛像上脱落的膜状残片的数据和六种蛋白质类胶结材料的数据进行解读,确定了膜状残片的蛋白质类有机材料为动物胶(骨胶或皮胶)和蛋清,证明PCA是一种有效的降维和可视化方法。本研究利用PCA技术对THM-Py-GC/MS数据进行分析解读,且结果可信,为之后该技术的发展提供新的契机。

    Abstract:

    Proteinaceous binding media, including animal glue, egg white, egg yolk and porcine blood, were widely used for organic cultural relics in China. Gas chromatography/mass spectrometry (GC/MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) are often used for their identification. According to literature reviews, marker compounds of animal glue and egg yolk are relatively clear, but those of egg white and porcine blood are still controversial. However, there is no further subdivision of animal glue in the literature, and marker compounds of egg yolk are consistent with other materials commonly used for ancient organic objects, such as wax, oil and lacquer, which makes it difficult to identify egg yolk in complex ancient objects. In our study, thermally assisted hydrolysis-methylation pyrolysis-gas chromatography/mass spectrometry (THM-Py-GC/MS) was used to analyze six kinds of proteinaceous binding media—bone glue, hide glue, fish maw glue, egg white, egg yolk and porcine blood—which were commonly used for ancient murals, paintings and other cultural relics. Their spectra were analyzed according to the RAdICAL system developed by the Getty Conservation Institute, and their characteristic pyrolysis products were also summarized. The results show that 1) pyrroles, especially pyrrole, diketodipyrrole and diketopiperazines can be used as recognition components of bone glue and hide glue; 2) besides pyrroles mentioned above, recognition components of fish maw glue also include cholesterols; 3) indoles, blood/egg white marker compounds, prolines and trimethyl phosphate are recognition components of egg white and porcine blood, and cholesterol compounds are also recognition components of porcine blood in addition to the above four kinds of compounds; 4) recognition components of egg yolk are trimethyl phosphate, egg yolk marker and cholesterols. According to this method and data interpretation, the six common proteinaceous binding materials in cultural relics were successfully recognized and distinguished, which gives support to solving archaeological problems and conserving cultural relics. Finally, principal component analysis (PCA) was used to interpret data of the six proteinaceous binding materials and a piece of film from a sculpture of Avalokitesvara Bodhisattva of Longshan Temple in Anhai County, Quanzhou, Fujian Province. It was determined that the proteinaceous materials of the film were animal glue (bone glue or hide glue) and egg white. In our study, PCA was used to interpret THM-Py-GC/MS data and presented a credible result in the field of archaeometry and cultural relic conservation. This study, to a certain extent, has solved the problem of identifying proteinaceous binding media in organic cultural objects. Six kinds of proteinaceous binding media were successfully identified using THM-Py-GC/MS, and their data were reinterpreted using PCA. Visual classification of the six kinds of proteinaceous binding media was realized. The methods were successfully applied to an ancient Bodhisattva sculpture, providing a new opportunity for their development.

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  • 收稿日期:2021-10-28
  • 最后修改日期:2022-04-21
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  • 在线发布日期: 2022-11-08
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