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首页> 外文期刊>The Analyst >When unfolding is better: unique success of unfolded partial least-squares regression with residual bilinearization for the processing of spectral–pH data with strong spectral overlapping. Analysis of fluoroquinolones in human urine based on flow-injection pH-modulated synchronous fluorescence data matrices
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When unfolding is better: unique success of unfolded partial least-squares regression with residual bilinearization for the processing of spectral–pH data with strong spectral overlapping. Analysis of fluoroquinolones in human urine based on flow-injection pH-modulated synchronous fluorescence data matrices

机译：当展开效果更好时：展开的部分最小二乘回归与残留双线性化的独特成功，可用于处理具有强光谱重叠的光谱-pH数据。基于流动注射pH调制同步荧光数据矩阵的人尿中氟喹诺酮类药物分析

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Synchronous fluorescence spectra measured in a flow-injection system with double pH gradientnmodulation constitute a new second-order signal which is herein studied for the quantitativendetermination of three fluoroquinolone antibiotics in spiked human urine samples. Because calibrationnis done using aqueous solutions of each of the three analytes ciprofloxacin, norfloxacin and ofloxacin,nthe fluorescent urine background makes it necessary to achieve the second-order advantage. Severalnsecond-order multivariate calibration algorithms were evaluated for this purpose: parallel factornanalysis, unfolded and multiway partial least-squares with residual bilinearization, and multivariatencurve resolution-alternating least-squares. The best analytical figures of merit, a root mean square errornof 4–6 mg Lu00021n(corresponding to a relative error of 4–6% for a calibration range from 0 to 200 mg Lu00021nfor each analyte), and a limit of detection of 4 mg Lu00021nwere obtained using partial least-squares (in thenspecific unfolded version) combined with residual bilinearization. Reasons for the improved success ofnthis latter technique are provided on the basis of the analysis of simulated second-order data.
机译：在具有双pH梯度调制的流动注射系统中测量的同步荧光光谱构成了一个新的二阶信号，在此进行了研究，用于定量测定加标的人类尿液样品中的三种氟喹诺酮抗生素。由于使用三种分析物环丙沙星，去甲沙星和奥沙星中的每一种的水溶液进行校准，因此，荧光尿液的本底背景有必要实现二级优势。为此，对几种二阶多元校准算法进行了评估：并行因子分析，具有残留双线性化的展开式和多元偏最小二乘法以及可变分辨率的最小二乘多元曲线。最佳性能指标，均方根误差n为4–6 mg Lu00021n（对应于从0至200 mg Lu00021n的校准范围，每种分析物的相对误差为4–6％），检出限为4 mg Lu00021n是通过使用局部最小二乘法（在特定的展开版本中）结合残差双线性化获得的。在对模拟的二阶数据进行分析的基础上，提供了后一种技术取得成功的原因。

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  • 来源
    《The Analyst》 |2009年第8期|p.1682-1691|共10页
  • 作者

    Mariano D. Borraccetti Patricia C. Damiani and Alejandro C. Olivieri;

  • 作者单位

    Departamento de Qu´ ımica Anal´ ıtica, Facultad de Ciencias Bioqu´ ımicas yFarmacu0002 euticas, Universidad Nacional de Rosario e Instituto de Qu´ ımicaRosario (IQUIR-CONICET), Suipacha 531, Rosario (2000),Argentina. E-mail: olivieri@iquir-conicet.gov.ar† Electronic supplementary information (ESI) available: algorithmdetails and figures of merit calculations. See DOI: 10.1039/b903649k;

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