Second-order based calibration methods have been widely investigated capitalizing on the inherent benefits of the data structure and the decomposition models, demonstrating that second-order advantage is a property that conspires to a high likelihood success in the resolution of systems of varying complexity. This work aims to demonstrate the applicability of a combined chemometric strategy to solve non-linear multivariate calibration systems in the presence of non-multilinear multi-way data. The determination of histamine by differential pulse voltammetry at different pH is presented as case study. The experimental system has the outstanding difficulty arisen from the large displacement along the potential axis by the pH, which was successfully overcome by implementation of the presented combined strategy. For data modeling, MCR-ALS, U-PLS/RBL and U-PCA/RBL-RBF were used. MCR-ALS allowed unraveling the non-linear behavior between the signal and the concentration, and extracting the underlying profiles of the constituent. Quantitative analysis was performed through the three models, and a comparative evaluation of the predictive performance was done. The best results were achieved with U-PCA/RBL-RBF (mean recovery = 101%) whereas, MCR-ALS yield the lowest mean recovery for all samples (70%).

中文翻译：

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探索结合化学计量学方法对具有定量目的的非线性多路数据进行建模的潜力——案例研究

基于二阶的校准方法已被广泛研究，利用数据结构和分解模型的固有优势，证明二阶优势是一种属性，有助于在不同复杂度的系统的解析中获得成功。这项工作旨在证明组合化学计量策略在存在非线性多路数据的情况下解决非线性多变量校准系统的适用性。通过差分脉冲伏安法在不同 pH 值下测定组胺作为案例研究。该实验系统具有由 pH 值沿势轴产生的大位移所引起的突出困难，通过实施所提出的组合策略成功地克服了这一困难。对于数据建模，MCR-ALS，使用 U-PLS/RBL 和 U-PCA/RBL-RBF。MCR-ALS 允许解开信号和浓度之间的非线性行为，并提取成分的基本轮廓。通过三个模型进行定量分析，并对预测性能进行了比较评估。U-PCA/RBL-RBF 获得了最好的结果（平均回收率 = 101%），而 MCR-ALS 的所有样品平均回收率最低（70%）。