Abstract The ultimate goal of the present study is to develop screening methodology for the urine analysis of metabolites of polycyclic aromatic hydrocarbons. The investigated approach is based on surface matrix fluorescence spectroscopy, where octadecyl silica membranes serve the dual purpose of metabolite extraction and solid substrate for fluorescence measurements. One of the main challenges faced by this approach is the interference of concomitants in the sample matrix. The present study focuses on three metabolites with strong spectral and lifetime overlapping, namely benzo[a]pyrene-trans-9,10-dihydrodiol, benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol and benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol. As an attempt to improve spectral and lifetime resolution, time-resolved excitation emission matrices are recorded at 77 K with the aid of a cryogenic fiber optic probe and laser-based instrumentation. In comparison to conventional spectrofluorimeters, the use of laser-based instrumentation improves the limits of detection by approximately two-orders of magnitude. The fiber optic probe facilitates the collection of time-resolved excitation emission matrices for the detection of the three metabolites at the pg mL− 1 concentration level. Their accurate determination in urine samples of unknwon composition is only possible with the aid of unfolded-partial least squares/residual tri-linearization. This algorithm demonstrated to be well-equipped to handle strong overlapping in both the spectral and time domains.

中文翻译：

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直接分析在光谱和寿命域中具有强烈重叠的苯并 [a] 芘代谢物

摘要 本研究的最终目标是开发多环芳烃代谢物尿液分析的筛查方法。所研究的方法基于表面基质荧光光谱，其中十八烷基二氧化硅膜具有代谢物提取和用于荧光测量的固体底物的双重目的。这种方法面临的主要挑战之一是样品基质中伴随物的干扰。本研究侧重于三种具有强烈光谱和寿命重叠的代谢物，即苯并[a]芘-反式-9,10-二氢二醇、苯并[a]芘-r-7,t-8,c-9-四氢三醇和苯并[a]芘-反式-9,10-二氢二醇[a]芘-r-7,t-8,c-9,c-10-四氢四醇。作为提高光谱和寿命分辨率的尝试，借助低温光纤探头和基于激光的仪器，在 77 K 下记录时间分辨激发发射矩阵。与传统的荧光分光计相比，使用基于激光的仪器将检测限提高了大约两个数量级。光纤探针有助于收集时间分辨激发发射矩阵，以检测 pg mL-1 浓度水平的三种代谢物。只有在未折叠偏最小二乘法/残差三线性化的帮助下，才能准确测定未知成分的尿液样本。该算法被证明能够很好地处理频谱和时域中的强重叠。与传统的荧光分光计相比，使用基于激光的仪器将检测限提高了大约两个数量级。光纤探针有助于收集时间分辨激发发射矩阵，以检测 pg mL-1 浓度水平的三种代谢物。只有在未折叠偏最小二乘法/残差三线性化的帮助下，才能准确测定未知成分的尿液样本。该算法证明能够很好地处理频谱和时域中的强重叠。与传统的荧光分光计相比，使用基于激光的仪器将检测限提高了大约两个数量级。光纤探针有助于收集时间分辨激发发射矩阵，以检测 pg mL-1 浓度水平的三种代谢物。只有在未折叠偏最小二乘法/残差三线性化的帮助下，才能准确测定未知成分的尿液样本。该算法证明能够很好地处理频谱和时域中的强重叠。光纤探针有助于收集时间分辨激发发射矩阵，以检测 pg mL-1 浓度水平的三种代谢物。只有在未折叠偏最小二乘法/残差三线性化的帮助下，才能准确测定未知成分的尿液样本。该算法证明能够很好地处理频谱和时域中的强重叠。光纤探针有助于收集时间分辨激发发射矩阵，以检测 pg mL-1 浓度水平的三种代谢物。只有在未折叠偏最小二乘法/残差三线性化的帮助下，才能准确测定未知成分的尿液样本。该算法被证明能够很好地处理频谱和时域中的强重叠。