Espinosa-Mansilla Anunciación, Muñoz de la Peña Arsenio, Goicoechea Hector C, Olivieri Alejandro C
Departamento de Química Analítica, Universidad de Extremadura, Badajoz, Spain.
Appl Spectrosc. 2004 Jan;58(1):83-90. doi: 10.1366/000370204322729504.
Two pesticides, carbaryl and chlorpyrifos, have been simultaneously determined using second-order kinetic spectrophotometric measurements upon alkaline oxidative degradation. In spite of the complexity of the system and of the serious spectral overlap among the reagents and products, calibration and prediction is possible thanks to the power of second-order multivariate techniques. Strategies such as parallel factor analysis (PARAFAC) and multivariate curve resolution coupled to alternating least-squares (MCR-ALS) have been employed, which adequately exploit the second-order advantage. They allow for a correct determination of the analytes both in synthetic binary samples and in a commercial formulation, in this latter case even in the presence of unmodeled interferents. Multi-way partial least-squares (n-PLS) produced good results only on synthetic binary mixtures but could not be applied to a commercial sample because it contained an uncalibrated component.
通过碱性氧化降解后的二阶动力学分光光度法同时测定了两种农药，西维因和毒死蜱。尽管该体系复杂，且试剂和产物之间存在严重的光谱重叠，但由于二阶多元技术的强大功能，校准和预测仍是可行的。已采用诸如平行因子分析（PARAFAC）和与交替最小二乘法相结合的多元曲线分辨（MCR-ALS）等策略，这些策略充分利用了二阶优势。它们能够在合成二元样品和商业制剂中正确测定分析物，在后一种情况下，即使存在未建模的干扰物也能做到。多元偏最小二乘法（n-PLS）仅在合成二元混合物上产生了良好结果，但无法应用于商业样品，因为该样品含有未校准的成分。
