文物中多糖类胶结材料的热裂解-气相色谱/质谱识别

doi:10.3724/SP.J.1123.2022.03005

摘要/Abstract

摘要：

热裂解-气相色谱/质谱(Py-GC/MS)技术能够实现微量样品中有机组分的准确、快速检测,非常适用于文物中各类天然有机材料的定性分析。该研究以中国古代书画、建筑、器物等文化遗产中常用的淀粉、桃胶,以及西方文化遗产中常用的阿拉伯胶等多糖类胶结材料为研究对象,系统分析并总结各类材料的Py-GC/MS特征裂解组分及辨别方法。研究发现,淀粉、桃胶、阿拉伯胶在色谱保留时间前段的裂解产物基本一致,主要是小分子呋喃、酮类组分;在保留时间中段3类材料的裂解产物主要是呋喃型酮等组分,但不同材料的具体裂解组分差异明显;在保留时间后段,3类材料检出多种单糖衍生物以及单糖低聚体衍生物,其中桃胶与阿拉伯胶裂解组分较为接近,但与淀粉完全不同。因此,可根据不同保留时间段淀粉、桃胶、阿拉伯胶裂解产物的差异实现3类材料的辨别,其中1,6-脱水-β-D-吡喃葡萄糖只在淀粉中检出且色谱峰强度高,可以作为识别淀粉的特征组分;此外,可根据桃胶、阿拉伯胶在保留时间后段的裂解产物主要质谱碎片离子m/z 60、m/z 101的提取离子流图分布特征实现其辨别。基于所建立的Py-GC/MS方法,研究推断故宫旧藏清代剔红云龙纹天球瓶瓶口部位黏结材料含有面粉,旻宁御笔并蒂含芳贴落画心纸所用黏结材料为面粉糨糊。该研究所建立方法及所总结的数据易于推广,适用于我国文物中多糖类材料的准确、快速识别,研究结果能为相关文物材质工艺的研究以及保护修复方案的制定提供科学依据。

关键词: 热裂解-气相色谱/质谱, 多糖, 胶结材料, 淀粉, 桃胶, 阿拉伯胶

Abstract:

Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) is suitable for the qualitative analysis of natural organic materials in cultural relics owing to its ability of accurately and rapidly identifying trace quantities of organic components in samples. In the present study, pyrolytic components of starch and peach gum, which are commonly used in ancient Chinese cultural relics such as calligraphic works, paintings, architecture, and objects, as well as gum Arabic, which is commonly used in western cultural relics, were systematically characterized using Py-GC/MS. As polysaccharide materials are often found mixed with other organic materials in cultural relics, an online methylation Py-GC/MS procedure previously established by the authors’ research group, which is suitable for the qualitative analysis of drying oils, proteins, and waxes, was performed to analyze the starch, peach gum, and gum Arabic reference samples. The established experimental procedure can be used to comprehensively analyze the polysaccharides and other organic materials in cultural relics owing to its slow heating rate, long running time, wide mass spectrometry detection range, and high chromatographic separation efficiency.

The experimental results were examined by dividing the pyrolytic products into three sections depending on the retention time. In the first section (2.5-10 min), pyrolytic products from the three sample types were similar and mostly included small molecule furans and ketones. However, the peach gum and gum Arabic contain a wider variety of pyrolytic products than starch, possibly because starch contains only glucose, whereas peach gum and gum Arabic contain a variety of monosaccharides. In the middle section (10-19 min), the pyrolytic products of starch, peach gum, and gum Arabic mostly consisted of furanones and other components. However, a unique profile was produced for each material type. Nevertheless, it should be noted that 2-methoxy-phenol and maltol were detected in all three materials with high chromatographic peak intensities. Therefore, these components are suitable markers for the identification of polysaccharides. In the last section (19-60 min), a variety of monosaccharide derivatives and monosaccharide oligomer derivatives were detected in the reference samples. The pyrolytic products of peach gum and gum Arabic were similar but completely different from those of starch. Therefore, starch, peach gum, and gum Arabic could be distinguished according to their pyrolytic products. In particular, 1,6-anhydro-β-D-glucopyranose was detected in starch with an extremely high intensity and was undetected in either of the other reference materials. Thus, this compound could act as a characteristic pyrolytic component for the identification of starch. Peach gum and gum Arabic could be rapidly distinguished according to the extracted ion chromatograms for m/z 60 and m/z 101, which represented major fragments of the pyrolytic products of peach gum and gum Arabic in the last section of the chromatogram.

The established Py-GC/MS method was successfully applied to the identification of starch in binding materials from the rim of a globular carved red lacquer vase with dragon and cloud motifs, as well as in paper collected from a Tieluo with Bingdihanfang written by Min-ning. Both objects are part of the Palace Museum collection and originate from the Qing Dynasty. Research results of the present work are easy to be popularized. This study provides a method suitable for the accurate and rapid identification of polysaccharide materials in cultural relics, as well as a scientific basis for the research, conservation, and restoration of similar cultural relics. However, it should be noted that aging and the presence of other organic or inorganic materials in cultural relics may interfere with the detection of polysaccharide materials. Therefore, a further investigation on the aging behavior of polysaccharides and the effects of other materials on the identification of polysaccharides is required.

Key words: pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), polysaccharides, binding material, starch, peach gum, gum Arabic

中图分类号:

O658

王娜, 谷岸, 屈雅洁, 雷勇. 文物中多糖类胶结材料的热裂解-气相色谱/质谱识别[J]. 色谱, 2022, 40(8): 753-762.

WANG Na, GU An, QU Yajie, LEI Yong. Identification of polysaccharide binding materials used in cultural relics by pyrolysis-gas chromatography/mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(8): 753-762.

图/表 12

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Sample	Glucose	Arabinose	Rhamnose	Galactose	Xylose	Mannose	Uronic acid
Starch^[25]	√
Peach gum^[26]		√	√	√	√	√	√
Gum Arabic^[27]		√	√	√

Sample	Glucose	Arabinose	Rhamnose	Galactose	Xylose	Mannose	Uronic acid
Starch^[25]	√
Peach gum^[26]		√	√	√	√	√	√
Gum Arabic^[27]		√	√	√

t_R/min	Pyrolytic component	Starch	Peach gum	Gum Arabic
2.9	3-methyl-furan	√	√	√
3.1	1-hydroxy-2-butanone		√	√
3.2	1,2-ethanediol monoacetate		√	√
3.3	succindialdehyde		√	√
3.5	1-deoxy-2,4-methylene-3,5-anhydro-D-xylitol			√
3.9	3-furaldehyde	√	√
4.2	2-(methoxymethyl)-furan			√
4.2	2-cyclopenten-1-one			√
4.3	furfural	√	√	√
4.7	2-butanone		√	√
4.8	2-furanmethanol	√	√	√
5.0	1-(acetyloxy)-2-propanone	√	√	√
5.4	cyclopent-4-ene-1,3-dione	√	√	√
5.6	2,5-dihydro-3,5-dimethyl-2-furanone			√
6.0	2-methyl-2-cyclopenten-1-one		√	√
6.1	1-(2-furanyl)-ethanone	√	√	√
6.2	2(5H)-furanone	√	√	√
6.5	1,2-cyclopentanedione	√	√	√
6.6	2,5-hexanedione		√	√
6.9	5-methyl-2(5H)-furanone		√	√
7.0	3-methyl-2,5-furandione	√
7.6	5-methyl-2-furancarboxaldehyde	√	√	√
7.7	1-(acetyloxy)-2-butanone	√	√	√
8.0	methyl 2-furoate		√	√
8.8	2,5-dihydro-3,5-dimethyl-2-furanone		√	√
9.5	2,2-dimethylpropanoic anhydride	√
9.7	3-methylcyclopentane-1,2-dione	√	√	√

t_R/min	Pyrolytic component	Starch	Peach gum	Gum Arabic
2.9	3-methyl-furan	√	√	√
3.1	1-hydroxy-2-butanone		√	√
3.2	1,2-ethanediol monoacetate		√	√
3.3	succindialdehyde		√	√
3.5	1-deoxy-2,4-methylene-3,5-anhydro-D-xylitol			√
3.9	3-furaldehyde	√	√
4.2	2-(methoxymethyl)-furan			√
4.2	2-cyclopenten-1-one			√
4.3	furfural	√	√	√
4.7	2-butanone		√	√
4.8	2-furanmethanol	√	√	√
5.0	1-(acetyloxy)-2-propanone	√	√	√
5.4	cyclopent-4-ene-1,3-dione	√	√	√
5.6	2,5-dihydro-3,5-dimethyl-2-furanone			√
6.0	2-methyl-2-cyclopenten-1-one		√	√
6.1	1-(2-furanyl)-ethanone	√	√	√
6.2	2(5H)-furanone	√	√	√
6.5	1,2-cyclopentanedione	√	√	√
6.6	2,5-hexanedione		√	√
6.9	5-methyl-2(5H)-furanone		√	√
7.0	3-methyl-2,5-furandione	√
7.6	5-methyl-2-furancarboxaldehyde	√	√	√
7.7	1-(acetyloxy)-2-butanone	√	√	√
8.0	methyl 2-furoate		√	√
8.8	2,5-dihydro-3,5-dimethyl-2-furanone		√	√
9.5	2,2-dimethylpropanoic anhydride	√
9.7	3-methylcyclopentane-1,2-dione	√	√	√

Sample	t_R/min	Pyrolytic component	Sample	t_R/min	Pyrolytic component
Starch	10.3	2-ethyl-2-hexen-1-ol	Gum Arabic	10.4	5-oxotetrahydrofuran-2-carboxylic acid
	11.6	2,5-dimethylfuran-3,4(2H,5H)-dione		11.7	2-methoxy-phenol
	11.7	2-methoxy-phenol		12.0	3-methyl-1,2-cyclopentanedione
	12.6	maltol		12.6	maltol
	13.8	2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one		13.1	5-acetyldihydro-2(3H)-furanone
	13.9	tetrahydro-2H-pyran-2-one		14.0	1-octen-3-yl-acetate
	15.1	5-(2-propynyloxy)-2-pentanol		14.1	4-methoxycarbonyl-4-butanolide
	15.4	3,5-dihydroxy-2-methyl-4H-pyran-4-one		14.2	1,4-dimethoxy-benzene
	16.1	1,4∶3,6-dianhydro-α-D-glucopyranose		15.0	2,6-anhydro-1,3,4-tri-O-methyl-β-D-
	16.3	2,3-anhydro-D-galactosan			fructofuranose
	16.5	2,3-anhydro-D-mannosan		15.7	5-oxotetrahydrofuran-2-carboxylic
	17.0	5-hydroxymethylfurfural			acid ethyl ester
Peach gum	10.2	4-methyl-5H-furan-2-one		15.8	di(5-methoxy-3-methylpent-2-yl)
	10.5	4,5-dimethyl-1,3-dioxol-2-one			glutaric acid ester
	10.6	3-ethyl-2-hydroxy-2-cyclopenten-1-one		16.2	4-methoxy-2,5-dimethyl-3(2H)-
	11.6	2,5-dimethylfuran-3,4(2H,5H)-dione			furanone
	11.7	2-methoxy-phenol		16.6	2-acetyl-5-methylfuran
	11.9	pentanal		17.1	4-(1-methylethyl)-2-cyclohexen-1-one
	12.0	3-methyl-1,2-cyclopentanedione
	12.6	maltol
	13.1	5-acetyldihydro-2(3H)-furanone
	13.9	dihydro-2H-pyran-2,6(3H)-dione
	15.1	5-(2-propynyloxy)-2-pentanol
	15.8	di(5-methoxy-3-methylpent-2-yl) glutaric acid ester
	16.9	4-methoxycarbonyl-4-butanolide
	18.1	1-(2,5-dihydroxyphenyl)-ethanone