College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, China.
College of Chemistry and Life Sciences, Chuxiong Normal University, Chuxiong, 675000, China.
Anal Bioanal Chem. 2019 Apr;411(10):2019-2029. doi: 10.1007/s00216-019-01624-5. Epub 2019 Feb 13.
A method that combines five-way fluorescence kinetics with fourth-order calibration for interference-free quantification of diclofenac sodium in river water was proposed and tested. Traditional fluorescence methods may not be suitable for such measurements since the fluorescence properties of the analyte are highly dependent on both pH and irradiation time in situ. In the method considered here, a five-way emission-excitation-time-pH data array was obtained from the samples by introducing the pH level and irradiation time as two extra modes. Then the data array was resolved by three fourth-order calibration algorithms: alternating fitting weighted residue quinquelinear decomposition (AFWRQQLD), five-way parallel factor analysis (five-PARAFAC), and alternating quinquelinear decomposition (AQQLD). The average recoveries and detection limits calculated for diclofenac sodium in a set of analyte-spiked river water samples using AFWRQQLD, five-PARAFAC, and AQQLD were 97.2 ± 3.2% and 1.9 ng mL, 96.8 ± 3.0% and 4.0 ng mL, and 92.6 ± 2.7% and 2.5 ng mL, respectively. A study of other figures of merit, statistical analysis, an elliptical joint confidence region test, and a t-test were additionally carried out to validate the analytical performance of the proposed method in detail. The results demonstrated that this new method required only two steps (fluorescence measurement and algorithm analysis) to determine the analyte concentration. It could therefore provide the basis for developing novel reliable and sensitive approaches for the accurate detection of pharmaceutical pollutants with unstable fluorescence properties in real complex matrices such as environmental water samples. Graphical Abstract ᅟ.
提出并测试了一种将五向荧光动力学与四阶校准相结合的方法，用于无干扰定量测定河水中的双氯芬酸钠。由于分析物的荧光性质在现场高度依赖于 pH 值和辐照时间，因此传统的荧光方法可能不适用于此类测量。在所考虑的方法中，通过引入 pH 值和辐照时间作为两个额外模式，从样品中获得了五向发射-激发-时间-pH 数据阵列。然后，通过三种四阶校准算法（交替拟合加权残差五线性分解（AFWRQQLD）、五向平行因子分析（five-PARAFAC）和交替五线性分解（AQQLD））对数据阵列进行解析。使用 AFWRQQLD、five-PARAFAC 和 AQQLD 计算的双氯芬酸钠在一组加标河水样品中的平均回收率和检测限分别为 97.2 ± 3.2%和 1.9 ng mL、96.8 ± 3.0%和 4.0 ng mL、92.6 ± 2.7%和 2.5 ng mL。此外，还进行了其他评价指标的研究、统计分析、椭圆联合置信区间检验和 t 检验，以详细验证所提出方法的分析性能。结果表明，该新方法仅需两步（荧光测量和算法分析）即可确定分析物浓度。因此，它可以为在真实复杂基质（如环境水样）中准确检测具有不稳定荧光性质的药物污染物提供开发可靠和敏感方法的基础。
