Chair and Department of Medicinal Chemistry, Faculty of Pharmacy, Medical University of Lublin, Jaczewskiego 4, 20-090 Lublin, Poland.
Chair and Department of Clinical and Experimental Pharmacology, Faculty of Medicine, Medical University of Lublin, Jaczewskiego 8b, 20-090 Lublin, Poland.
Molecules. 2021 Nov 21;26(22):7035. doi: 10.3390/molecules26227035.
This is an introductory tutorial and review about the uncertainty problem in chromatographic calibration. It emphasizes some unobvious, but important details influencing errors in the calibration curve estimation, uncertainty in prediction, as well as the connections and dependences between them, all from various perspectives of uncertainty measurement. Nonuniform D-optimal designs coming from Fedorov theorem are computed and presented. As an example, all possible designs of 24 calibration samples (3-8, 4-6, 6-4, 8-3 and 12-2, both uniform and D-optimal) are compared in context of many optimality criteria. It can be concluded that there are only two independent (orthogonal, but slightly complex) trends in optimality of these designs. The conclusions are important, as the uniform designs with many concentrations are not the best choices, contrary to some intuitive perception. Nonuniform designs are visibly better alternative in most calibration cases.
这是一篇关于色谱校准中不确定度问题的介绍性教程和综述。它强调了一些不明显但重要的细节，这些细节会影响校准曲线估计中的误差、预测中的不确定度，以及它们之间的联系和依赖性，所有这些都是从不确定性测量的不同角度来看的。根据费多罗定理计算并给出了非均匀 D-最优设计。例如，在多个最优性标准的背景下，比较了 24 个校准样品（3-8、4-6、6-4、8-3 和 12-2，包括均匀和 D-最优）的所有可能设计。可以得出结论，这些设计的最优性只有两个独立（正交，但稍微复杂）的趋势。这些结论很重要，因为与某些直观的看法相反，具有多个浓度的均匀设计并不是最佳选择。在大多数校准情况下，非均匀设计显然是更好的选择。
