title: Net analyte signal as a deconvolution-oriented resolution criterion in the optimisation of chromatographic techniques.
abstract: The performance of two multivariate calibration measurements, multivariate selectivity (SEL(s)) and scalar net analyte signal (scalar NAS), as chromatographic objective functions (COFs), was investigated. Since both assessments are straightforwardly related to the quantification of analytes in the presence of interferents, they were expected to confer new features in the optimisation of compound resolution, not present in conventional assessments. These capabilities are especially interesting in situations of low resolution, where peak deconvolution becomes an attractive alternative. For comparison purposes, chromatographic resolution (R(s)) and peak purity (p(s)) were used as reference COFs. In order to correlate COFs with the probability of deconvolution error, an artificial peak crossing was used to generate 73 different peak arrangements, which were deconvolved using three different methods. SEL(s) exhibited the best correlation, which allowed predicting properly the risk of obtaining inaccurate deconvolutions. The optimisation of a poorly resolved mixture of 16 aromatic compounds by reversed-phase liquid chromatography with methanol-water and acetonitrile-water mobile phases was examined to investigate the differences in performance among the resolution criteria. In situations like these, SEL(s) tends to consider acceptable mobile phase compositions with partial coelution, which permits however the deconvolution with low errors. In contrast, p(s) selects compositions where the resolution of some compounds is sacrificed to enhance the separation of others. Scalar NAS was not so favourable as expected, since it depends on sampling frequency and peak widening. SEL(s) was not affected by these factors.
authors.affiliation: Departament de Química Analítica, Facultat de Química, Universitat de València, 46100 Burjassot, València, Spain.
authors.forename: G
authors.initials: G
authors.lastname: Vivó-Truyols
authors.forename: J R
authors.initials: JR
authors.lastname: Torres-Lapasió
authors.forename: M C
authors.initials: MC
authors.lastname: García-Alvarez-Coque
mesh_terms: D000097:Acetonitriles; D002138:Calibration; D002845:Chromatography / Q000379:methods* / Q000592:standards; D002851:Chromatography, High Pressure Liquid / Q000379:methods; D006841:Hydrocarbons, Aromatic / Q000032:analysis* / Q000737:chemistry; D000432:Methanol; D008962:Models, Theoretical; D015999:Multivariate Analysis; D012997:Solvents; D014867:Water
chemical_list: D000097:Acetonitriles; D006841:Hydrocarbons, Aromatic; D012997:Solvents; D014867:Water; D000432:Methanol; C032159:acetonitrile