Abstract In this work, the generation and posterior chemometric resolution of third-order data, obtained from samples processed by liquid chromatography (LC) with online registering of excitation-emission fluorescence matrices (EEM) is reported. Samples were instrumentally processed in a relatively short time, and neither an intentional reduction of the linear flow rate nor an unconventional fluorescence instrument were required. Through the inclusion of external circuitry based on open-source hardware, the occurrence time of each individual fluorescence intensity reading was recorded. For the reported instrumental setup, irregular signal sampling was verified. In order to consider samples-specific time measurements, the PARAFAC (Parallel Factor Analysis) algorithm, and the derived APARAFAC (Augmented-PARAFAC) strategy, were adapted. The functional information was employed during the computational stages, through the development and implementation of smoothing strategies. To tackle differences between the rate of spectral acquisition and the rate of change in the concentration of the mobile fluorophores, Expectation Maximization was implemented. Data from samples with one calibrated analyte (Vitamin B6-Pyridoxine), in presence of uncalibrated interferents, were modeled. In order to preserve the original data structure, unfolding data operations were minimized. The resolved profiles of all species were in agreement with the corresponding chromatographic and spectral references. Results suggest that the effects derived from the loss of trilinearity previously reported in the literature for LC-EEM data, depend on interpretation and subsequent modeling of the data. The reported strategies can be useful with other flow techniques and kinetics.

中文翻译：

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液相色谱数据的光谱-时间依赖性的化学计量处理，在线注册激发-发射荧光矩阵

摘要 在这项工作中，报告了三阶数据的生成和后验化学计量分辨率，这些数据是从液相色谱 (LC) 处理的样品中获得的，并具有激发发射荧光矩阵 (EEM) 的在线配准。样品在相对较短的时间内进行仪器处理，既不需要有意降低线性流速，也不需要非常规的荧光仪器。通过包含基于开源硬件的外部电路，记录了每个单独荧光强度读数的发生时间。对于报告的仪器设置，验证了不规则的信号采样。为了考虑特定于样本的时间测量，对 PARAFAC（并行因子分析）算法和派生的 APARAFAC（Augmented-PARAFAC）策略进行了调整。在计算阶段，通过平滑策略的开发和实施，使用了功能信息。为了解决光谱采集速率与移动荧光团浓度变化速率之间的差异，实施了期望最大化。对含有一种校准分析物（维生素 B6-吡哆醇）、存在未校准干扰物的样品的数据进行建模。为了保留原始数据结构，展开数据操作被最小化。所有物种的解析谱与相应的色谱和光谱参考一致。结果表明，先前在 LC-EEM 数据文献中报告的三线性损失所产生的影响取决于数据的解释和随后的建模。