QSPR models of boiling point, octanol–water partition coefficient and retention time index of polycyclic aromatic hydrocarbons

Abstract A Quantitative Structure–Property Relationship (QSPR) analysis and study of polycyclic aromatic hydrocarbons (PAHs) is presented. Three physicochemical properties related to their environmental impact are studied: boiling point (bp), octanol–water partition coefficient ( log K ow ) and retention time index (RI) for reversed-phase liquid chromatography analysis. The geometry of all PAHs were optimized by the semi-empirical method AM1 and used to calculate thermodynamic, electronic, steric and topological descriptors: HOMO and LUMO energies and the GAP between them, molecular hardness, polarizability, atomic charges, connectivity index, volume and surface area among others. After variable selection, principal component regression (PCR) and partial least squares (PLS) with leave-one-out crossvalidation were used for building the regression models. The regression coefficients obtained for the models were 0.995 (PCR and PLS) for bp, 0.975 (PCR) and 0.976 (PLS) for log K ow , and 0.898 (PCR and PLS) for RI. Finally, the models were used to predict these properties for those compounds for which experimental measurements are still unknown.

[1]  J. Dearden,et al.  QSAR study of the toxicity of benzoic acids to Vibrio fischeri, Daphnia magna and carp. , 1998, The Science of the total environment.

[2]  S. Huling,et al.  Dense nonaqueous-phase liquids. Ground-water issue , 1991 .

[3]  N. Bodor,et al.  Nitrogen radical cations as intermediates in enzymatically mediated oxidative deaminations—application of molecular parametric models , 1995 .

[4]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[5]  P. Geladi.  Notes on the history and nature of partial least squares (PLS) modelling , 1988 .

[6]  Han van de Waterbeemd,et al.  Chemometric methods in molecular design , 1995 .

[7]  Ana Elisa,et al.  AVALIAÇÃO DA CONTAMINAÇÃO HUMANA POR HIDROCARBONETOS POLICÍCLICOS AROMÁTICOS (HPAS) E SEUS DERIVADOS NITRADOS (NHPAS): UMA REVISÃO METODOLÓGICA , 2000 .

[8]  Marina Lasagni,et al.  New molecular descriptors for 2D and 3D structures. Theory , 1994 .

[9]  W. Hehre.  Experiments in computational organic chemistry , 1993 .

[10]  H. Kubinyi.  QSAR : Hansch analysis and related approaches , 1993 .

[11]  Eamonn F. Healy,et al.  Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model , 1985 .

[12]  B. Kowalski,et al.  Partial least-squares regression: a tutorial , 1986 .

[13]  J. Ross.  Ullman's encyclopedia of industrial chemistry , 1986 .

[14]  M. Cronin,et al.  Validation of Vibrio fisheri acute toxicity data: mechanism of action-based QSARs for non-polar narcotics and polar narcotic phenols. , 1997, The Science of the total environment.

[15]  Márcia M. C. Ferreira,et al.  Polycyclic aromatic hydrocarbons: a QSPR study. Quantitative structure-property relationships. , 2001, Chemosphere.

[16]  M. Randic.  Novel molecular descriptor for structure—property studies , 1993 .

[17]  H. Wiener.  Structural determination of paraffin boiling points. , 1947, Journal of the American Chemical Society.

[18]  Curt M. White,et al.  Prediction of the boiling point, heat of vaporization, and vapor pressure at various temperatures for polycyclic aromatic hydrocarbons , 1986 .

[19]  M. Randic.  Characterization of molecular branching , 1975 .

[20]  P. Labute.  A widely applicable set of descriptors. , 2000, Journal of molecular graphics & modelling.

[21]  Paola Gramatica,et al.  SD-modelling and Prediction by WHIM Descriptors. Part 5. Theory Development and Chemical Meaning of WHIM Descriptors , 1997 .

[22]  Eñaut Urrestarazu Ramos,et al.  Quantitative Structure−Activity Relationships for the Aquatic Toxicity of Polar and Nonpolar Narcotic Pollutants , 1998 .

[23]  H. B. Krop,et al.  n-Octanol-water partition coefficients, aqueous solubilities and Henry's law constants of fatty acid esters , 1997 .

[24]  W. Karcher,et al.  Spectral atlas of polycyclic aromatic compounds , 1988 .

[25]  Paola Gramatica,et al.  Weighted holistic invariant molecular descriptors. Part 2. Theory development and applications on modeling physicochemical properties of polyaromatic hydrocarbons , 1995 .

[26]  N. Bodor,et al.  Theoretical study of the stereoisomers of tetrahydrocannabinols , 1997 .

[27]  Maria Fernanda Pimentel e Benício de Barros Neto.  Calibração: Uma Revisão para Químicos Analíticos , 1996 .

[28]  W. Shiu,et al.  Illustrated handbook of physical-chemical properties and environmental fate for organic chemicals. Volume 5: pesticide chemicals. , 1992 .

[29]  Mati Karelson,et al.  QSPR Prediction of Densities of Organic Liquids , 1999, Comput. Chem..

[30]  J. W. Flesher,et al.  BENZYLIC CARBONIUM IONS AS ULTIMATE CARCINOGENS OF POLYNUCLEAR AROMATIC HYDROCARBONS , 1996 .

[31]  Saikia Arupjyoti,et al.  New Electrotopological Descriptor for Prediction of Boiling Points of Alkanes and Aliphatic Alcohols Through Artificial Neural Network and Multiple Linear Regression Analysis , 1998, Comput. Chem..

[32]  L. Burkhard,et al.  Estimation of vapor pressures for polychlorinated biphenyls: a comparison of eleven predictive methods. , 1985, Environmental science & technology.

[33]  J. Hermens,et al.  Classifying environmental pollutants. 2: Separation of class 1 (baseline toxicity) and class 2 (‘polar narcosis’) type compounds based on chemical descriptors , 1996 .

[34]  Márcia M. C. Ferreira,et al.  Estudo do coeficiente de partição octanol-água de bifenilas policloradas (PCBs) utilizando parâmetros topológicos , 2003 .