| Surface-enhanced Raman spectroscopy(SERS)is widely used in interface science,pharmaceutical,chemical and environmental sanitation because of its high sensitivity,overcoming fluorescence,and fast and convenient detection.In recent years,along with the rise of archaeology and the complex,low content and easy degradation of dyes in textile relics,its identification has always been a difficult point in the field of cultural relics analysis.SERS technology is applied to the detection and analysis of dyes on textile relics.The identification of dye components helps us to understand the history of dyes,dyeing processes and provide theoretical basis for the protection and repair of cultural relics.In this study,the prepared SERS substrate was characterized by confocal micro-Raman spectroscopy and field emission scanning electron microscopy.SERS technology and in situ non-extraction hydrolysis method were used to detect and analyze the ancient natural dye standards,modern textile dyes and ancient textile dyes,and the results of the test are supported by density functional theory and high performance liquid chromatography-mass spectrometry.The main research covers the following aspects.(1)The three different ways were prepared for SERS activity substrate.The metal nanosilver colliods substrate with different particle size and shape is prepared by reducing the silver nitrate by sodium citrate;the silver film substrate deposited on the glass piece is prepared by the principle of silver mirror reaction;the method of magnetron sputtering is utilized.A silver film substrate deposited on a glass slide was prepared.The preparation of the three substrates is simple,the preparation cost is low,the substrate is convenient to use and the pollution is small.(2)For the first time,we systematically studied the SERS spectra of twenty ancient commonly used natural dyes at different excitation wavelengths(532,633,785 nm)using three SERS substrates and identified the natural dyes by density functional theory(DFT).The Raman peak displacement belongs.The results show that the silver colliods substrate has a better enhancement effect and the SERS enhancement effect of the natural dye at different excitation wavelengths is different.The experimental values of the SERS spectra of the collected natural dyes are in agreement with the theoretical values.Compared with the silver nanocolliods substrate,the natural dyes collected by the two silver film substrates have poorer spectra and the SERS enhancement effect is weaker.(3)Silver nanocolliods were used as the SERS substrate to detect and analyze modern textile dyes,and to understand the dyeing history and dyeing process of several commonly used natural dyes.The results show that the red dye safflower had a weak Raman signal;the main dyes in the yellow dye glutinous rice were quercetin and rutin;the madder of red dye had four leaves and six leaves,and it contained different amounts of alizarin and purpurin;The red color dye hemp can dye different colors in the pre-mord and post-mord process and the dye molecular structure is not destroyed.(4)The nanosilver colliods was used as the SERS substrate,combined with the in-situ non-extraction hydrolysis method,and the ancient textile relics were detected and analyzed.The sampling amount was 2mm when tested,and the dosage was one-fifth of the conventional detection method.The test result shows that the textile cultural relics in Xinjiang Yingpan have natural dyes such as alizarin and pupurin.The Hall of Mental Cultivation of textile relics are dyed by natural dyes Sophora japonica and Rhamnus petiolaris.In Lop Nurland the remaining textile relics are dyed by ellagic acid and madeder.The yellow part of the robes of the Qing Dynasty detected quercetin and rutin,so it was mainly Sophora japonica dyeing.For thousand years ago the cotton fiber unearthed in the Middle East contains red dye alizarin and pupurin.T`he 1700-year-old The embroidered floral sleeves red part of the head is dyed by the four-leaf clover. |
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