Alam Todd M, Alam M Kathleen, McIntyre Sarah K, Volk David E, Neerathilingam Muniasamy, Luxon Bruce A
Department of Electronic and Nanostructured Materials, Sandia National Laboratories, Albuquerque, New Mexico 87185-0886, USA.
Anal Chem. 2009 Jun 1;81(11):4433-43. doi: 10.1021/ac900262g.
The implementation of direct standardization (DS), piecewise direct standardization (PDS), and double-window piecewise direct standardization (DWPDS) instrumental transfer techniques for high-resolution (1)H NMR spectral data was explored. The ability to transfer a multivariate calibration model developed for a "master or target" NMR instrument configuration to seven different ("secondary") NMR instrument configurations was measured. Partial least-squares (PLS) calibration of glucose, glycine, and citrate metabolite relative concentrations in model mixtures following mapping of the secondary instrumental configurations using DS, PDS, or DWPDS instrumental transfer allowed the performance of the different transfer methods to be assessed. Results from these studies suggest that DS and PDS transfer techniques produce similar improvements in the error of prediction compared to each other and provide a significant improvement over standard spectral preprocessing techniques including reference deconvolution and spectral binning. The DS instrumental transfer method produced the largest percent improvement in the predictions of concentrations for these model mixtures but, in general, required that additional transfer calibration standards be used. Limitations of the different instrumental transfer methods with respect to sample subset selection are also discussed.
探索了用于高分辨率¹H NMR光谱数据的直接标准化（DS）、分段直接标准化（PDS）和双窗口分段直接标准化（DWPDS）仪器转移技术的实施。测量了将为“主或目标”NMR仪器配置开发的多元校准模型转移到七种不同的（“二级”）NMR仪器配置的能力。在使用DS、PDS或DWPDS仪器转移对二级仪器配置进行映射后，对模型混合物中葡萄糖、甘氨酸和柠檬酸盐代谢物相对浓度进行偏最小二乘（PLS）校准，从而可以评估不同转移方法的性能。这些研究结果表明，与彼此相比，DS和PDS转移技术在预测误差方面产生了相似的改进，并且与包括参考去卷积和光谱分箱在内的标准光谱预处理技术相比有显著改进。DS仪器转移方法在这些模型混合物浓度预测方面产生的改进百分比最大，但一般来说，需要使用额外的转移校准标准。还讨论了不同仪器转移方法在样本子集选择方面的局限性。
