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基于偏最小二乘多元校正法的流通式荧光传感测定仪测定α-和β-萘酚混合物

A flow-through fluorimetric sensing device for determination of alpha- and beta-naphthol mixtures using a partial least-squares multivariate calibration approach.

机构信息

Faculty of Experimental Sciences, Department of Physical and Analytical Chemistry, University of Jaén, Paraje Las Lagunillas ED 5, E-23071 Jaén, Spain.

出版信息

Talanta. 2003 Jun 13;60(2-3):313-23. doi: 10.1016/S0039-9140(03)00110-3.

Abstract

A single flow-through optosensor spectrofluorimetric system is proposed for the resolution of mixtures of alpha- and beta-naphthol at mug l(-1) levels using a partial least-squares (PLS) calibration approach. The sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorimetric detection using Sephadex QAE A-25 resin as an active sorbent substrate in the flow cell and the second derivative of the native synchronous fluorescence spectra of analytes as analytical signal. In the manifold, the solutions of naphthol (at pH 10.0) were injected in a carrier stream of KCl (0.15 M)/NaOH (10(-2) M). Because of the strong spectral overlap, the mixture could not be resolved by conventional spectrofluorimetry. The non-additive behaviour of the fluorescence signals revealed an interaction in the system, which was not found by working in the solution only (without the sorbent support). This interaction, probably due to the environment of the analytes on the solid phase, made impossible their simultaneous determination. So, the use of synchronous fluorescence spectroscopy or even its derivative signal could not resolve satisfactorily the mixture. The simultaneous determination of both naphthol has been carried out by recording the signal of the second-derivative synchronous fluorescence (Deltalambda=170 nm) spectra between 200 and 450 nm and a PLS multivariate calibration treatment. The optimum number of factors was selected by using the cross-validation method. After validating the proposed method, it was applied to the determination of these compounds in natural waters with different amounts of each chemical.

摘要

提出了一种单通流路光学生物传感器分光光度系统,用于在微克/升(μg/L)水平下通过偏最小二乘法(PLS)校准方法分辨α-和β-萘酚混合物。该传感器与单通道流动注射分析系统结合使用,在流池内使用 Sephadex QAE A-25 树脂作为活性吸附剂基质,采用分析物的天然同步荧光光谱二阶导数作为分析信号,进行荧光检测。在该流路中,将萘酚溶液(pH 10.0)注入 KCl(0.15 M)/NaOH(10^-2 M)载流中。由于光谱强烈重叠,常规分光荧光法无法分辨混合物。荧光信号的非加和行为表明体系存在相互作用,而仅在溶液中(无吸附剂支持)工作时并未发现这种相互作用。这种相互作用可能是由于分析物在固相中所处的环境所致,使得它们无法同时测定。因此,即使使用同步荧光光谱法甚至其导数信号,也无法令人满意地分辨混合物。通过记录 200 到 450nm 之间二阶导数同步荧光(Delta lambda=170nm)光谱的信号,并采用 PLS 多元校准处理,实现了同时测定两种萘酚。通过交叉验证法选择最佳因子数。在验证了所提出的方法后,将其应用于不同化学物质含量的天然水中这些化合物的测定。

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