Departamento de Química Analítica, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario and Instituto de Química Rosario (IQUIR-CONICET), Suipacha 531, Rosario (S2002LRK), Argentina.
Anal Chem. 2012 Oct 16;84(20):8697-706. doi: 10.1021/ac3019284. Epub 2012 Sep 25.
A new equation is derived for estimating the sensitivity when the multivariate curve resolution-alternating least-squares (MCR-ALS) method is applied to second-order multivariate calibration data. The validity of the expression is substantiated by extensive Monte Carlo noise addition simulations. The multivariate selectivity can be derived from the new sensitivity expression. Other important figures of merit, such as limit of detection, limit of quantitation, and concentration uncertainty of MCR-ALS quantitative estimations can be easily estimated from the proposed sensitivity expression and the instrumental noise. An experimental example involving the determination of an analyte in the presence of uncalibrated interfering agents is described in detail, involving second-order time-decaying sensitized lanthanide luminescence excitation spectra. The estimated figures of merit are reasonably correlated with the analytical features of the analyzed experimental system.
当多元曲线分辨-交替最小二乘法（MCR-ALS）方法应用于二阶多元校准数据时，推导出了一个新的灵敏度估算方程。通过广泛的蒙特卡罗噪声添加模拟验证了该表达式的有效性。可以从新的灵敏度表达式中推导出多元选择性。其他重要的质量指标，如检测限、定量限和 MCR-ALS 定量估计的浓度不确定度，可以很容易地从提出的灵敏度表达式和仪器噪声中估算出来。详细描述了一个涉及在未校准的干扰剂存在下测定分析物的实验实例，涉及二阶时间衰减敏化镧系元素荧光激发光谱。估计的质量指标与分析实验系统的分析特征合理相关。
