摘要
三维荧光光谱因其数据量大、灵敏度高等优点,在食品科学、分析化学、生物化学和环境科学等领域应用广泛。然而,因为同时存在瑞利散射和拉曼散射,给三维荧光光谱的定量分析和数据显示带来了困难。因此,在数据处理前期,消除散射干扰对其具有重要意义。在已有方法中,对较低浓度溶液和散射峰与物质荧光信号重叠严重光谱的去散射算法的研究相对空白。针对现有问题,提出了一种自适应的三维荧光光谱去散射方法。首先,该方法通过减去每次实验获取的溶剂的光谱基线来校正拉曼散射和背景干扰。然后综合考虑散射峰与物质峰的荧光强度和重叠程度将光谱分为五类情况对应三个重叠等级:无重叠、微弱重叠和严重重叠,分别采用置零法、分段三次Hermite插值多项式算法和高斯拟合-分段三次Hermite插值多项式耦合算法对瑞利散射进行校正处理。此方法基于一维插值,仅对单个发射光谱进行研究,降低了算法复杂度,计算时间较短。通过对酪氨酸、黄腐酸、萘乙酸和罗丹明B四种典型有机化合物进行实验,评估了该方法扣除散射干扰的有效性。并且与现阶段研究中使用最多的Delaunay三角形内插值法进行比较,以重叠区域散射校正后的数据对四种有机化合物分别进行浓度回归,此自适应方法所得的平均决定系数为0.9962,相比于Delaunay三角形内插值法提高了5.04%。同时,通过对比天然有机化合物黄腐酸分别经此方法和Delaunay三角形内插值法进行散射校正后的三维荧光光谱,进一步证明了该方法更好地保持了物质荧光光谱区域的结构特征,有效地避免了过拟合现象的发生。最后,利用该方法对模拟突发污染水样进行监测,验证了此方法具有很好的普适性,有实际应用价值,为三维荧光光谱去散射提供了一种新的思路。
Excitation-emission matrix spectroscopy(EEMs)was widely used in food science,analytical chemistry,biochemistry and environmental science because of its wealth of information and high sensitivity.However,the Rayleigh and Raman scatterings bring difficulties to display data and quantitative analysis of EEMs.Therefore,in the early stage of data processing,eliminating the scatterings interference is significant for the popularization and application of EEMs.In previous studies,few researchers aimed to deal with the low-concentration solution and the scattering peaks overlap with the material fluorescence signals.In order to solve this problem,the paper proposed a self-adapting method to remove the scatterings of EEMs.First,the method corrects the Raman scatterings and background interference by subtracting the spectral baseline of the solvent obtained in each experiment.Then,according to the intensity and overlap degree of fluorescence signals and scattering peaks.EEMs are divided into five categories corresponding to three overlap levels:no overlap,weak overlap and serious overlap.The Rayleigh scatterings are corrected by setting to zero,piecewise cubic Hermite interpolation polynomial algorithm and Gaussian-piecewise cubic Hermite interpolation polynomial coupling algorithm,respectively.The method is based on one-dimensional interpolation,and only emission spectrums are studied,reducing the algorithm s complexity and computation time.The method s effectiveness was demonstrated by the experiments on four typical organic compounds:Tyrosine,Fulvic acid,Naphthalene acetic acid and Rhodamine B.Moreover,compared with the Delaunay interpolation method,which is most used in current research.The concentration regressions are performed with the EEMs after the scatterings correction;the average of-R-squared obtained by the method is 0.9962,which is 5.04%higher than the Delaunay interpolation method.At the same time,by comparing the EEMs of Fulvic acid corrected by the method and Delaunay interpolation method,it is proved that
作者
伍卓慧
黄冰佳
李学勤
王晓萍
WU Zhuo-hui;HUANG Bing-jia;LI Xue-qin;WANG Xiao-ping(Ocean College,Zhejiang University,Zhoushan 316021,China;Hainan Institute of Zhejiang University,Sanya 572025,China;The Engineering Research Center of Oceanic Sensing Technology and Equipment,Ministry of Education,Zhoushan 316021,China)
出处
《光谱学与光谱分析》
SCIE
EI
CAS
CSCD
北大核心
2024年第4期969-976,共8页
Spectroscopy and Spectral Analysis
基金
浙江省“尖兵”“领雁”研发攻关计划项目(2022C03027)
国家自然科学基金项目(52171340)资助。
关键词
三维荧光光谱
瑞利散射
拉曼散射
自适应
去散射
Excitation-emission matrix spectroscopy
Rayleigh scatterings
Raman scatterings
A self-adapting method
Removing scatterings
