Department of Chemistry, University of Central Florida, Orlando, FL 32816, USA.
Catedra de Quimica Analitica I, Facultad de Bioquimica y Ciencias Biologicas, Universidad Nacional del Litoral, Ciudad Universitaria, CC 242-S30001 Santa Fe, Argentina.
Anal Chim Acta. 2014 Feb 6;811:60-9. doi: 10.1016/j.aca.2013.12.004. Epub 2013 Dec 11.
An attractive approach to handle matrix interference in samples of unknown composition is to generate second- or higher-order data formats and process them with appropriate chemometric algorithms. Several strategies exist to generate high-order data in fluorescence spectroscopy, including wavelength time matrices, excitation-emission matrices and time-resolved excitation-emission matrices. This article tackles a different aspect of generating high-order fluorescence data as it focuses on total synchronous fluorescence spectroscopy. This approach refers to recording synchronous fluorescence spectra at various wavelength offsets. Analogous to the concept of an excitation-emission data format, total synchronous data arrays fit into the category of second-order data. The main difference between them is the non-bilinear behavior of synchronous fluorescence data. Synchronous spectral profiles change with the wavelength offset used for sample excitation. The work presented here reports the first application of total synchronous fluorescence spectroscopy to the analysis of monohydroxy-polycyclic aromatic hydrocarbons in urine samples of unknown composition. Matrix interference is appropriately handled by processing the data either with unfolded-partial least squares and multi-way partial least squares, both followed by residual bi-linearization.
处理未知成分样品中基质干扰的一种有吸引力的方法是生成二阶或更高阶的数据格式，并使用适当的化学计量学算法对其进行处理。在荧光光谱学中，有几种生成高阶数据的策略，包括波长时间矩阵、激发-发射矩阵和时间分辨激发-发射矩阵。本文探讨了生成高阶荧光数据的一个不同方面，因为它侧重于全同步荧光光谱学。这种方法是指在不同的波长偏移处记录同步荧光光谱。类似于激发-发射数据格式的概念，全同步数据数组属于二阶数据。它们之间的主要区别在于同步荧光数据的非线性行为。同步光谱轮廓随用于样品激发的波长偏移而变化。这里介绍的工作首次将全同步荧光光谱学应用于分析未知成分尿液样品中的单羟基多环芳烃。通过使用未展开部分最小二乘法和多向部分最小二乘法处理数据，并随后进行残余双线性化，可以适当处理基质干扰。
