Resolution of overlapped non-absorbing and absorbing solutes using either an absorption null-balance detection window or multivariate deconvolution applied to capillary electrophoresis of anionic surfactants

Non-absorbing alkyl ether sulfates (AES) can be separated using anthraquinone-2-carboxylic acid (AQCA) as a probe; however, absorbing alkyl benzene sulfortates (ABS), if present, interfere indirect detection of most AES oligomers. Overcoming of this interference, as well as the simultaneous characterisation and evaluation of AES, fatty acids and ABS, was accomplished by using a diode-array detector and the procedures here discussed. First, it was shown that ABS can be made undetectable by using a 9 nm wide and 227 nm centred charge-absorptivity null-balance detection window (NBDW), where its contribution to the absorbance cancels the dilution effects that its presence induces on the signal of the background chromophore (BGC). Two other procedures, not requiring any prior knowledge on the nature of the absorbing interference, were also addressed. In the first one, the NBDW procedure was emulated by software, by treating the time-wavelength data matrix stored during the experimental run, and in the second one, both the ABS and BGC spectra, and the concentration profiles of ABS and the non-absorbing solutes, were recovered by orthogonal projection approach (OPA) and alternating least squares (ALS). The OFA-ALS processing provided the deconvolved signals and the wavelengths required to implement the experimental and software-emulated NBDW procedures. A composite ABS spectrum and a mixed concentration profile of the non-absorbing solutes, that involves mutual ABS-BGC dilution effects are enclosed in the OPA-ALS straightforward solutions. The pure spectra and concentration profiles were finally retrieved by crossed orthogonalisation. For the NBDW procedures, the limits of detection (S/N = 3) for AES oligomers overlapped by 1500 mug ml(-1) ABS were of ca. 10 muM AES. Using decyl sulfate as internal standard, the relative standard deviation for AES in an ABS containing industrial sample was 4.5%. The procedures here described are useful to remove the interference produced by any absorbing solute when overlapped with indirectly detected solutes in both capillary electrophoresis (CE) and HPLC. (C) 2004 Elsevier B.V. All rights reserved.