Ratiometric SERS quantification of SO2 vapor based on Au@Ag-Au with Raman reporter as internal standard

Yu Lu; Xiufang Mo; Geng Zhu; Yan Huang; Yingchao Wang; Zhenzhong Yang; Liqiong Gao; Guofang Shen; Yi Wang; Xiangwei Zhao

doi:10.1016/j.jhazmat.2024.133763

Ratiometric SERS quantification of SO₂ vapor based on Au@Ag-Au with Raman reporter as internal standard

J Hazard Mater. 2024 Apr 5:467:133763. doi: 10.1016/j.jhazmat.2024.133763. Epub 2024 Feb 11.

Authors

Yu Lu¹, Xiufang Mo¹, Geng Zhu¹, Yan Huang¹, Yingchao Wang², Zhenzhong Yang³, Liqiong Gao⁴, Guofang Shen⁴, Yi Wang⁵, Xiangwei Zhao⁶

Affiliations

¹ State Key Laboratory of Digital Medical Engineering, School of Biological Science and Medical Engineering, Southeast University, Nanjing 211189, China; Institute of Biomaterials and Medical Devices, Southeast University, Suzhou 215163, China; Southeast University Shenzhen Research Institute, Shenzhen 518000, China.
² Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China; Innovation Institute for Artificial Intelligence in Medicine of Zhejiang University, Hangzhou 310018, China.
³ Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China.
⁴ Hangzhou Institute for Food and Drug Control, Hangzhou 310022, China.
⁵ Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China; Innovation Institute for Artificial Intelligence in Medicine of Zhejiang University, Hangzhou 310018, China. Electronic address: zjuwangyi@zju.edu.cn.
⁶ State Key Laboratory of Digital Medical Engineering, School of Biological Science and Medical Engineering, Southeast University, Nanjing 211189, China; Institute of Biomaterials and Medical Devices, Southeast University, Suzhou 215163, China; Southeast University Shenzhen Research Institute, Shenzhen 518000, China. Electronic address: xwzhao@seu.edu.cn.

PMID: 38359757
DOI: 10.1016/j.jhazmat.2024.133763

Abstract

Practical gas sensing application requires sensors to quantify target analytes with high sensitivity and reproducibility. However, conventional surface enhanced Raman scattering (SERS) sensor lacks reproducibility and quantification arising from variations of "hot spot" distribution and measurement conditions. Here, a ratio-dependent SERS sensor was developed for quantitative label-free gas sensing. Au@Ag-Au nanoparticles (NPs) were filtered onto anodic aluminum oxide (AAO) forming Au@Ag-Au@AAO SERS substrate. 4-MBA was encapsulated in the gap of Au@Ag-Au and served as the internal standard (IS) to calibrate SERS signal fluctuation for improved quantification ability. Combined with headspace sampling method, SO₂ residue in traditional Chinese medicine (TCM) can be extracted and captured on the immediate vicinity of Au@Ag-Au surface. The intensity ratio I_{613 cm}^_-1/I_{1078 cm}^_-1 showed excellent linearity within the range of 0.5 mg/kg-500 mg/kg, demonstrating superior quantification performance for SO₂ detection. Signals for concentration as low as 0.05 mg/kg of SO₂ could be effectively collected, much lower than the strictest limit 10 mg/kg in Chinese Pharmacopoeia. Combined with a handheld Raman spectrometer, handy and quantitative TCM quality evaluation in aspect of SO₂ residue was realized. This ratiometric SERS sensor functioned well in rapid on-site SO₂ quantification, exhibiting excellent sensitivity and simple operability.

Keywords: Internal standard (IS); Quantitative detection; Sulfur dioxide; Surface enhanced Raman scattering (SERS).

MeSH terms

Gold / chemistry
Medicine, Chinese Traditional
Metal Nanoparticles* / chemistry
Reproducibility of Results
Silver / chemistry

Substances

Gold
Silver