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基于光镊 - 激光诱导击穿光谱和机器学习的单个微米级悬浮颗粒中银纳米粒子增强铜元素的定量分析

Quantitative Analysis of the Cu Element Enhanced by AgNPs in a Single Microsized Suspended Particle Based on Optical Trapping-LIBS and Machine Learning.

作者信息

Chen Tingting, Zhang Tianlong, Tang Hongsheng, Cheng Xuemei, Li Hua

机构信息

Key Laboratory of Synthetic and Natural Functional Molecular Chemistry of Ministry of Education, College of Chemistry & Material Science, Northwest University, Xi'an, 710127, China.

Technology and Nano Functional Materials, Institute of Photonics & Photon-Technology, Northwest University, Xi'an 710127, PR China.

出版信息

Anal Chem. 2023 Mar 14;95(10):4819-4827. doi: 10.1021/acs.analchem.3c00487. Epub 2023 Mar 1.

Abstract

Extremely severe and persistent particulate pollution caused by industrialization and urbanization impacts air quality, regional and global climates, and human health. The unstable and complex spectral signal of laser-induced breakdown spectroscopy (LIBS) with minimal feature information and interference signals considerably influences the accuracy of qualitative and quantitative analysis. In response to overcome this phenomenon, in this work, quantitative analysis of Cu element enhanced by silver nanoparticles (AgNPs) in a single microsized suspended particle was proposed herein using optical trapping-LIBS and machine learning method was proposed. Initially, the optimal AgNPs enhancement conditions were optimized. The LIBS spectra of 15 polluted black carbon samples were collected and various spectral pretreatment methods were compared to optimize the LIBS spectra. Variable selection methods include variable importance measurement (VIM), variable importance projection (VIP), VIM-successive projections algorithm (VIM-SPA), VIM-genetic algorithm (VIM-GA), and VIM-mutual information (VIM-MI). Finally, several hybrid variable selection methods were implemented in random forest (RF) calibration models. In particular, a wavelet transform (WT)-VIM-SPA-RF calibration model has constructed under the WT spectral pretreatment method and the selected and optimized input variables (VIM-SPA). Results elucidate that the WT-VIM-SPA-RF calibration model ( = 0.9858, MREP = 0.0396) have the best prediction performance than the WT-RF and Raw-RF models in predicting the Cu level in a single microsized black carbon particle. Compared to the WT-RF and Raw-RF models, MREP values decreased by 37% and 62%, respectively. The values of RSD, RPD, and RER of this calibration model are 2.8%, 8.39%, and 17.79%, respectively. The aforementioned results demonstrate that the WT-VIM-SPA-RF calibration model with accuracy, stability, and robustness is a promising approach for improving the quantitative accuracy of the Cu level in carbon black particles.

摘要

工业化和城市化导致的极其严重且持续的颗粒物污染影响空气质量、区域和全球气候以及人类健康。激光诱导击穿光谱(LIBS)不稳定且复杂的光谱信号特征信息极少且存在干扰信号,这极大地影响了定性和定量分析的准确性。为应对并克服这一现象,本文提出利用光镊-LIBS对单个微米级悬浮颗粒中银纳米颗粒(AgNPs)增强的铜元素进行定量分析,并提出了机器学习方法。首先,优化了AgNPs的最佳增强条件。收集了15个污染黑碳样品的LIBS光谱,并比较了各种光谱预处理方法以优化LIBS光谱。变量选择方法包括变量重要性度量(VIM)、变量重要性投影(VIP)、VIM-连续投影算法(VIM-SPA)、VIM-遗传算法(VIM-GA)和VIM-互信息(VIM-MI)。最后,在随机森林(RF)校准模型中实施了几种混合变量选择方法。特别是,在小波变换(WT)光谱预处理方法和选定并优化的输入变量(VIM-SPA)下构建了小波变换(WT)-VIM-SPA-RF校准模型。结果表明,在预测单个微米级黑碳颗粒中的铜含量时,WT-VIM-SPA-RF校准模型(R = 0.9858,MREP = 0.0396)比WT-RF和原始RF模型具有更好的预测性能。与WT-RF和原始RF模型相比,MREP值分别降低了37%和62%。该校准模型的RSD、RPD和RER值分别为2.8%、8.39%和17.79%。上述结果表明,具有准确性、稳定性和鲁棒性的WT-VIM-SPA-RF校准模型是提高炭黑颗粒中铜含量定量准确性的一种有前途的方法。

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