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[拉曼光谱在古代文物染料鉴定中的研究进展]

[Research Progress of Raman Spectroscopy on Dyestuff Identification of Ancient Relics and Artifacts].

作者信息

He Qiu-ju, Wang Li-qin

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2016 Feb;36(2):401-7.

Abstract

As the birthplace of Silk Road, China has a long dyeing history. The valuable information about the production time, the source of dyeing material, dyeing process and preservation status were existed in organic dyestuff deriving from cultural relics and artifacts. However, because of the low contents, complex compositions and easily degraded of dyestuff, it is always a challenging task to identify the dyestuff in relics analyzing field. As a finger-print spectrum, Raman spectroscopy owns unique superiorities in dyestuff identification. Thus, the principle, characteristic, limitation, progress and development direction of micro-Raman spectroscopy (MRS/µ-Raman), near infrared reflection and Fourier transform Raman spectroscopy (NIR-FT-Raman), surface-enhanced Raman spectroscopy (SERS) and resonance raman spectroscopy (RRS) have been introduced in this paper. Furthermore, the features of Raman spectra of gardenia, curcumin and other natural dyestuffs were classified by MRS technology, and then the fluorescence phenomena of purpurin excitated with different wavelength laser was compared and analyzed. At last, gray green silver colloidal particles were made as the base, then the colorant of madder was identified combining with thin layer chromatography (TLC) separation technology and SERS, the result showed that the surface enhancement effect of silver colloidal particles could significantly reduce fluorescence background of the Raman spectra. It is pointed out that Raman spectroscopy is a rapid and convenient molecular structure qualitative methodology, which has broad application prospect in dyestuff analysis of cultural relics and artifacts. We propose that the combination of multi-Raman spectroscopy, separation technology and long distance transmission technology are the development trends of Raman spectroscopy.

摘要

作为丝绸之路的发源地,中国拥有悠久的染色历史。文物和手工艺品中的有机染料蕴含着有关生产时间、染色材料来源、染色工艺和保存状况的宝贵信息。然而,由于染料含量低、成分复杂且易降解,在文物分析领域鉴定染料一直是一项具有挑战性的任务。拉曼光谱作为一种指纹光谱,在染料鉴定方面具有独特的优势。因此,本文介绍了显微拉曼光谱(MRS/µ-Raman)、近红外反射和傅里叶变换拉曼光谱(NIR-FT-Raman)、表面增强拉曼光谱(SERS)和共振拉曼光谱(RRS)的原理、特点、局限性、进展和发展方向。此外,利用MRS技术对栀子、姜黄素等天然染料的拉曼光谱特征进行了分类,并对不同波长激光激发的紫红素荧光现象进行了比较分析。最后,以灰绿色银胶体颗粒为基底,结合薄层色谱(TLC)分离技术和SERS鉴定了茜草色素,结果表明银胶体颗粒的表面增强效应可显著降低拉曼光谱的荧光背景。指出拉曼光谱是一种快速便捷的分子结构定性方法,在文物和手工艺品染料分析中具有广阔的应用前景。提出多拉曼光谱、分离技术和长距离传输技术相结合是拉曼光谱的发展趋势。

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