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Modelling by partial least squares the relationship between the HPLC mobile phases and analytes on phenyl column
Author(s) -
Markopoulou Catherine K.,
Kouskoura Maria G.,
Koundourellis John E.
Publication year - 2011
Publication title -
journal of separation science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.72
H-Index - 102
eISSN - 1615-9314
pISSN - 1615-9306
DOI - 10.1002/jssc.201100091
Subject(s) - analyte , chemistry , chromatography , lipophilicity , partial least squares regression , column (typography) , analytical chemistry (journal) , polarizability , quantitative structure–activity relationship , mathematics , statistics , stereochemistry , molecule , organic chemistry , geometry , connection (principal bundle)
Twenty‐five descriptors and 61 structurally different analytes have been used on a partial least squares (PLS) to latent structure technique in order to study chromatographically their interaction mechanism on a phenyl column. According to the model, 240 different retention times of the analytes, expressed as Y variable (log k ), at different % MeOH mobile‐phase concentrations have been correlated with their theoretical most important structural or molecular descriptors. The goodness‐of‐fit was estimated by the coefficient of multiple determinations r 2 (0.919), and the root mean square error of estimation (RMSEE=0.1283) values with a predictive ability ( Q 2 ) of 0.901. The model was further validated using cross‐validation (CV), validated by 20 response permutations r 2 (0.0, 0.0146), Q 2 (0.0, −0.136) and validated by external prediction. The contribution of certain mechanism interactions between the analytes, the mobile phase and the column, proportional or counterbalancing is also studied. Trying to evaluate the influence on Y of every variable in a PLS model, VIP (variables importance in the projection) plot provides evidence that lipophilicity (expressed as Log D , Log P ), polarizability, refractivity and the eluting power of the mobile phase are dominant in the retention mechanism on a phenyl column.