纺织学报 ›› 2019, Vol. 40 ›› Issue (03): 76-82.doi: 10.13475/j.fzxb.20180305807

• 染整与化学品 • 上一篇    下一篇

表面增强拉曼光谱对纺织品文物中茜素和茜紫素的快速检测

陈磊1, 裴克梅1, 康晓静2, 李文瑛2, 赵丰3, 刘剑3()   

  1. 1.浙江理工大学 化学系, 浙江 杭州 310018
    2.新疆文物考古研究所, 新疆 乌鲁木齐 830011
    3.中国丝绸博物馆, 浙江 杭州 310002
  • 收稿日期:2018-03-23 修回日期:2018-12-13 出版日期:2019-03-15 发布日期:2019-03-15
  • 通讯作者: 刘剑
  • 作者简介:陈磊(1992—),男,硕士生。主要研究方向为用表面增强拉曼光谱技术检测分析古代纺织品染料。
  • 基金资助:
    国家自然科学基金资助项目(21673208);浙江省文物保护科技项目(2017002);浙江省自然科学基金资助项目(LY16B070009)

Rapidly detection of alizarin and purpurin in textile relics by surface-enhanced Raman spectroscopy

CHEN Lei1, PEI Kemei1, KANG Xiaojing2, LI Wenying2, ZHAO Feng3, LIU Jian3()   

  1. 1. Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. Xinjiang Institute of Relics and Archaeology, Urumqi, Xinjiang 830011, China
    3. China National Silk Museum, Hangzhou, Zhejiang 310002, China
  • Received:2018-03-23 Revised:2018-12-13 Online:2019-03-15 Published:2019-03-15
  • Contact: LIU Jian

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摘要：

为快速检测古代纺织品文物中的天然色素并达到无损分析的目的,采用表面增强拉曼光谱技术(SERS)对纺织品文物中天然染料茜素和茜紫素进行鉴定。以纳米银溶胶为SERS基底检测茜素和茜紫素的标准品,利用密度泛函理论计算结果对茜素和茜紫素分子的SERS光谱进行确认,分析得到茜素和茜紫素的SERS光谱在3种激发波长下的差异,并找出判断茜素和茜紫素存在的特征峰。在此基础上,从纺织品文物中提取1根长度约为2 mm的纤维,采用原位非萃取水解方法对其进行预处理,并进行SERS检测。结果表明,出土于新疆营盘的纺织品文物中红色染料成分是茜素和茜紫素。

关键词: 表面增强拉曼光谱, 茜素, 茜紫素, 纺织品文物, 密度泛函理论

Abstract:

In order to quickly detect natural pigments in ancient relics and achieve non-destructive analysis, surface-enhanced Raman spectroscopy(SERS) was adopted to rapidly identify natural dyes of alizarin and purpurin in textile relic samples. Silver colliod was adopted a substrate to detect alizarin and purpurin standard. The SERS spectra of alizarin and purpurin were identified detailed by the density functional theory. The difference of SERS spectra of alizarin and purpurin at three excitation wavelengths was analyzed, and the characteristic peaks for judging the presence of alizarin and purpurin were found. Based on the SERS of alizarin and purpurin standard, extracting a fiber about 2 mm long in the textile relics. After pretreatment of cultural fiber by in situ non-extraction hydrolysis method, SERS technology was used for the detection. The results shows that the red dye components in the textile relics which are unearthed in Xinjiang's Yingpan plate are alizarin and purpurin.

Key words: surface-enhanced Raman spectroscopy, alizarin, purpurin, textile relic, density function theory

中图分类号: 

  • O652.1

图1

银溶胶的场发射扫描电镜照片"

图2

银溶胶紫外-可见吸收光谱图"

图3

茜素标准品在3种激发波长下的SERS光谱"

图4

茜紫素标准品在3种激发波长下的SERS光谱"

图5

由DFT计算的茜素和茜紫素最稳定几何结构"

表1

茜素振动光谱的实验值和计算值以及振动模式"

序号 拉曼位移实验值/cm-1 振动模式 拉曼位移计算值/cm-1
V1 343(w) 面外弯曲振动C19C7C9C8[24%],面外弯曲振动O25C11C21C24[30%] 340
V2 479(w) 弯曲振动C8C9C11[20%], 弯曲振动C24C21C7[23%] 476
V3 581(vw) 弯曲振动O22C21C24[14%], 弯曲振动C4C5C6[26%] 585
V4 633(vw) 弯曲振动C9C11C24[14%] ,弯曲振动O25C24C11[15%] 624
V5 662(vw) 弯曲振动C4C5C6[13%],弯曲振动C1C5C6[20%] 674
V6 681(sh) 扭绞振动C3C2C1C6[11%],面外弯曲振动O15C11C21C24[14%] 676
V7 819(w) 扭绞振动H12C1C6C5[17%], 面外弯曲振动O18C4C7C17[17%] 812
V8 900(w) 弯曲振动C1C6C5[13%], 弯曲振动O20C19C8[18%] 909
V9 1 016(m) 扭绞振动H15C6C5C4[23%], 扭绞振动H12C1C6C5[28%] 1 015
V10 1 049(m ) 伸缩振动C19C8[13%], 伸缩振动C1C6[15%] 1 037
V11 1 161(m) 伸缩振动C9C11[17%], 弯曲振动H16C11C9[21%] 1 179
V12 1 189(w) 弯曲振动H12C1C6[12%],弯曲振动H13C2C1[29%] 1 192
V13 1 206(w) 伸缩振动C7C17[10%], 弯曲振动H10C9C11[15%] 1 216
V14 1 291(s ) 弯曲振动H13C2C1[11%],弯曲振动H14C5C6[18%] 1 298
V15 1 324(s) 伸缩振动C2C1[12%],伸缩振动C19C8[26%] 1 324
V16 1 419(s) 伸缩振动C21C7[10%], 弯曲振动H23O22C21[34%] 1 399
V17 1 457(w) 伸缩振动C8C9[24%], 弯曲振动H26O25C24[35%] 1 459
V18 1 552(w ) 伸缩振动O18C17[14%], 弯曲振动H10C9C11[16%] 1 530
V19 1 601(w) 弯曲振动C3C2C1[15%],伸缩振动C1C6[29%] 1 627

表2

茜紫素振动光谱的实验值和计算值以及振动模式"

序号 拉曼位移实验值/cm-1 振动模式 拉曼位移计算值/cm-1
V1 423(w) 弯曲振动C7C16C4[12%], 弯曲振动O26C9C10[20%] 423
V2 452(w) 弯曲振动C23C20C7[24%], 弯曲振动C8C9C10[27%] 457
V3 609(m) 弯曲振动C4C5C6[13%], 弯曲振动C9C10C23[19%] 607
V4 650(m) 扭绞振动H15C10C23C20[10%],面外弯曲振动O26C8C10C9[38%] 644
V5 905(w) 弯曲振动C18C8C9[11%],弯曲振动O19C18C8[17%] 914
V6 970(s) 伸缩振动C18C8[11%], 伸缩振动C8C9[13%] 986
V7 1 064(m) 伸缩振动C6C5[16%], 伸缩振动C1C6[32%] 1 057
V8 1 154(m) 弯曲振动H13C5C6[10%],伸缩振动C9C10[10%] 1 177
V9 1 211(m) 伸缩振动O26C9[13%],弯曲振动H15C10C23[46%] 1 219
V10 1 290(s ) 伸缩振动C16C4[13%] 1 291
V11 1 321(s) 弯曲振动H25O24C23[13%] 1 317
V12 1 391(s,br) 伸缩振动C16C4[12%], 伸缩振动C7C16[13%] 1 393
V13 1 471(m) 弯曲振动H11C1C6[10%],弯曲振动H14C6C5[11%] 1 499

图6

纺织品文物的表征"

图7

文物纤维在激发波长下的SERS谱图"

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