Hayashi Yuzuru, Matsuda Rieko
National Institute of Health Sciences, Setagaya, Tokyo, Japan.
Anal Sci. 2006 Jun;22(6):889-94. doi: 10.2116/analsci.22.889.
The traditional method for linear calibration can estimate the confidence intervals of calibration lines from a set of experimental data for a single calibration line. However, the following situations, often encountered in laboratories, are out of reach of the method, since the concentrations of the standard solutions are not independent of each other: (A) a standard solution is diluted from a more concentrated one in a stepwise way (stepwise dilution); (B) every standard solution for a calibration experiment is prepared from a stock solution, but the stock solution is newly prepared for each calibration (separate dilution with the variable concentration of the stock solution). This paper puts forward a theory to calculate the confidence intervals of calibration lines in the above situations. Analyses made up of sample weighing, dilution, HPLC measurement and calibration with the linear least-squares fitting are taken as examples. The proposed theory is numerically compared to the traditional method.
传统的线性校准方法可以根据一组针对单一校准曲线的实验数据来估计校准曲线的置信区间。然而,实验室中经常遇到以下情况,该方法无法适用,因为标准溶液的浓度并非相互独立:(A)一种标准溶液由浓度更高的溶液逐步稀释(逐步稀释);(B)校准实验的每种标准溶液均由储备溶液配制而成,但每次校准都新配制储备溶液(储备溶液浓度可变的单独稀释)。本文提出一种理论,用于计算上述情况下校准曲线的置信区间。以由样品称重、稀释、高效液相色谱测量以及线性最小二乘法拟合校准组成的分析为例。将所提出的理论与传统方法进行数值比较。