title: Quantitative structure-retention relationships applied to liquid chromatography gradient elution method for the determination of carbonyl-2,4-dinitrophenylhydrazone compounds.
abstract: A usual method for the determination of aldehydes and ketones in different matrices consists of a derivatization with 2,4-dinitrophenylhydrazine (DNPH) followed by HPLC-UV analysis. In the present work, a HPLC-UV gradient elution method has been applied to the analysis of 13 aldehydes and ketones-DNPH in automotive emission samples. In addition to these 13 compounds-DNPH, several carbonyl-DNPH compounds (linear, ramified and cyclic, saturated and unsaturated compounds) have been analyzed by HPLC-UV. Quantitative structure-retention relationships (QSRR) methods have been applied to predict the logarithm of capacity factor (logk') of carbonyl-DNPH compounds. According to its physicochemical meaning, combinations of 2 and 3 molecular descriptors have been proposed in order to achieve higher correlation with logk'. Using linear and non-linear QSRR methodologies, the resulting prediction models allowed the screening of the most probable carbonyl-DNPH derivative candidates that correspond to unknown compounds detected in automotive emission samples. This information has been useful for their identification by UPLC(®)-MS/MS. In addition, the chromatographic retention of different carbonyl-DNPH compound families was studied using two HPLC isocratic methods working with two orthogonal stationary phases (octadecylpolyethoxysilane and cyanopropyl). Differences between the retention indexes obtained for each column were used for classifying carbonyl-DNPH into compounds families.
authors.affiliation: Department of Analytical Chemistry, Chromatography Section, IQS (Institut Químic de Sarrià) - Universitat Ramon Llull, Via Augusta 390, 08017 Barcelona, Catalonia, Spain. elisenda.cirera@iqs.url.edu
authors.forename: Elisenda
authors.initials: E
authors.lastname: Cirera-Domènech
authors.forename: Roger
authors.initials: R
authors.lastname: Estrada-Tejedor
authors.forename: Francesc
authors.initials: F
authors.lastname: Broto-Puig
authors.forename: Jordi
authors.initials: J
authors.lastname: Teixidó
authors.forename: Miquel
authors.initials: M
authors.lastname: Gassiot-Matas
authors.forename: Lluís
authors.initials: L
authors.lastname: Comellas
authors.forename: Josep Lluís
authors.initials: JL
authors.lastname: Lliberia
authors.forename: Alberto
authors.initials: A
authors.lastname: Méndez
authors.forename: Susanna
authors.initials: S
authors.lastname: Paz-Estivill
authors.forename: Maria Rosa
authors.initials: MR
authors.lastname: Delgado-Ortiz
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D006835:Hydrazones / Q000032:analysis*; D021281:Quantitative Structure-Activity Relationship
chemical_list: D006835:Hydrazones