title: Retention behavior of isomeric polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography.
abstract: Retention indices for 70 polycyclic aromatic sulfur heterocycles (PASHs) were determined using reversed-phase liquid chromatography (LC) on a monomeric and a polymeric C18 stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Correlations between the retention on the polymeric C18 phase and PASH geometry (L/B and T) were investigated for six specific PASH isomer groups with molecular mass (MM) 184Da, 234Da, 258Da, 284Da, 334Da, and 384Da. Similar to previous studies for polycyclic aromatic hydrocarbons (PAHs), PASH elution order on the polymeric C18 phase was generally found to follow increasing L/B values. Correlation coefficients for retention vs L/B ranged from r=0.45 (MM 184Da) to r=0.89 (MM 284Da). In the case of smaller PASHs (MM≤258Da), the location of the sulfur atom in the bay-region of the structure resulted in later than expected elution of these isomers based on L/B. In the case of the larger PASHs (MM≥284Da), nonplanarity had a significant influence on earlier than predicted elution based on L/B values.
authors.affiliation: Chemical Sciences Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, United States. Electronic address: walter.wilson@nist.gov.
authors.forename: Walter B
authors.initials: WB
authors.lastname: Wilson
authors.affiliation: Chemical Sciences Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, United States.
authors.forename: Lane C
authors.initials: LC
authors.lastname: Sander
authors.affiliation: Chemical Sciences Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, United States.
authors.forename: Miren Lopez
authors.initials: ML
authors.lastname: de Alda
authors.affiliation: Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, United States.
authors.forename: Milton L
authors.initials: ML
authors.lastname: Lee
authors.affiliation: Chemical Sciences Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, United States.
authors.forename: Stephen A
authors.initials: SA
authors.lastname: Wise
mesh_terms: D056148:Chromatography, Reverse-Phase / Q000379:methods*; D007536:Isomerism; D008970:Molecular Weight; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry* / Q000302:isolation & purification*; D013455:Sulfur / Q000737:chemistry* / Q000302:isolation & purification
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; D013455:Sulfur
keywords: Molecular descriptors; Polycyclic aromatic compounds; Polycyclic aromatic sulfur heterocycles; Retention behavior; Retention indices; Reversed-phase liquid chromatography stationary phases