SHINERS in cultural heritage: Can SHINERS spectra always be compared with normal Raman spectra? A study of alizarin and its adsorption in the silicon dioxide shell,Journal of Raman Spectroscopy

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SHINERS in cultural heritage: Can SHINERS spectra always be compared with normal Raman spectra? A study of alizarin and its adsorption in the silicon dioxide shell
Journal of Raman Spectroscopy ( IF 2.4 ) Pub Date : 2021-06-08 , DOI: 10.1002/jrs.6172
Thiago Sevilhano Puglieri _{1,

2} , Odile Madden ₂ , Gustavo F. S. Andrade ₃

Affiliation

Raman microspectroscopy is a powerful analytical technique in cultural heritage. However, results are often compromised by luminescence interference and poor sensitivity. Surface-enhanced Raman spectroscopy (SERS) is an alternative that can enhance the Raman signal and quench luminescence, but the interaction of an analyte and metal substrate produces altered Raman spectra. Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) is a promising modification of SERS that encases the metal nanoparticles in ultrathin inert shells. As a consequence, it is reported that SHINERS spectra can be directly compared with normal Raman spectra, but this is not always the case, as discussed in this work. SHINERS, SERS, and normal Raman spectra were obtained from alizarin. The resulting spectra showed that the SHINERS data are comparable with the normal Raman spectrum of alizarin adsorbed in silica, not that of isolated alizarin. The structure of alizarin adsorbed in silica is discussed. Luminescence quenching observed in the SHINERS spectra can be attributed both to LSPR of the metallic nanoparticle cores and to alizarin–silica shell chemisorption. Both silica-encapsulated silver and gold nanoparticles were considered, and it is shown that SHINERS spectra are dependent on the interaction of alizarin with silica, rather than the specific metal core within, in contrast to our observations of Ag and Au SERS nanoparticles. The metal agnostic quality of SHINERS is a potential advantage for the collection and comparison of reference data. Additionally, SHINERS systems result in quite stable spectra in pHs ranging from, at least, 6.0 to 9.3. Future research directions for SHINERS in cultural heritage are also discussed.

中文翻译：

文化遗产中的 SHINERS：SHINERS 光谱是否总能与普通拉曼光谱进行比较？茜素及其在二氧化硅壳中的吸附研究

拉曼显微光谱是一种强大的文化遗产分析技术。然而，结果往往受到发光干扰和灵敏度差的影响。表面增强拉曼光谱 (SERS) 是一种可以增强拉曼信号和淬灭发光的替代方法，但分析物和金属底物的相互作用会产生改变的拉曼光谱。壳隔离纳米粒子增强拉曼光谱 (SHINERS) 是一种很有前途的 SERS 改进方法，它将金属纳米粒子包裹在超薄惰性壳中。因此，据报道可以直接将 SHINERS 光谱与正常拉曼光谱进行比较，但情况并非总是如此，正如本工作中所讨论的那样。SHINERS、SERS 和正常拉曼光谱是从茜素中获得的。所得光谱表明，SHINERS 数据与吸附在二氧化硅中的茜素的正常拉曼光谱相当，而不是分离的茜素。讨论了吸附在二氧化硅中的茜素的结构。在 SHINERS 光谱中观察到的发光猝灭可归因于金属纳米颗粒核的 LSPR 和茜素-二氧化硅壳化学吸附。二氧化硅包封的银和金纳米粒子都被考虑在内，与我们对银和金 SERS 纳米粒子的观察相反，它表明 SHINERS 光谱取决于茜素与二氧化硅的相互作用，而不是其中的特定金属核。SHINERS 的金属不可知质量是收集和比较参考数据的潜在优势。此外，SHINERS 系统在 pH 值范围内产生相当稳定的光谱，至少，6.0 到 9.3。还讨论了 SHINERS 在文化遗产方面的未来研究方向。

更新日期：2021-08-13

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