title: Experimental determination of LSER parameters for a set of 76 diverse pesticides and pharmaceuticals.
abstract: Linear solvation energy relationships (LSERs) have more recently been proposed as the method of choice to describe and/or predict the partitioning behavior of neutral organic compounds over a large range of environmental matrices and for a broad variety of compounds in a consistent manner. However, when dealing with more complex, polar compounds with multiple functional groups, it has also been noted that there is a severe lack of substance descriptors quantifying the different intermolecular interactions that these compounds may undergo. In this study, we used a system of eight reversed phase, normal phase, and hydrophilic interaction HPLC systems to determine the substance descriptors for H-bond donor (A) and acceptor (B) interactions and for polarizability and dipolarity (S) for a set of 76 complex compounds containing multiple functional groups, comprising mainly pesticides and some pharmaceuticals. The obtained substance descriptors for most compounds are unique in that values of A, S, and B are high and lie at the very upper end of the numerical range of currently known substance descriptors. The substance descriptors have been cross-compared against literature values of the octanol-water (Kow) and air-water (Kaw) partition coefficients and against a set of heptan-methanol partition coefficients (Khm) experimentally determined with a consistent methodology herein. The comparison confirmed plausibility of the substance descriptors of all except six tested compounds. The newly determined substance descriptors promise to be highly valuable in chemicalfate modeling, allowing, in conjunction with available phase descriptors, for a better representation of partitioning of polar compounds in those models. The results also reveal a systematic deviation of the log Kow values predicted with our substance descriptors from the literature values. The deviation points toward a possible problem when existing LSER equations are applied to polar, multifunctional compounds with high values of A, S, and B. Hence, the substance descriptors determined herein should also be helpful in revisiting the validity of existing LSERs for complex, polar compounds.
authors.affiliation: Institute ofBiogeochemistry and Pollutant Dynamics, ETH Zürich, CH-8092 Zürich, Switzerland.
authors.forename: Holger C
authors.initials: HC
authors.lastname: Tülp
authors.forename: Kai-Uwe
authors.initials: KU
authors.lastname: Goss
authors.forename: René P
authors.initials: RP
authors.lastname: Schwarzenbach
authors.forename: Kathrin
authors.initials: K
authors.lastname: Fenner
mesh_terms: D020003:1-Octanol / Q000737:chemistry; D000388:Air; D002851:Chromatography, High Pressure Liquid; D004785:Environmental Pollutants / Q000737:chemistry*; D006536:Heptanes / Q000737:chemistry; D000432:Methanol / Q000737:chemistry; D010575:Pesticides / Q000737:chemistry*; D004364:Pharmaceutical Preparations / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D014867:Water / Q000737:chemistry
chemical_list: D004785:Environmental Pollutants; D006536:Heptanes; D010575:Pesticides; D004364:Pharmaceutical Preparations; D012997:Solvents; D014867:Water; C028618:n-heptane; D020003:1-Octanol; D000432:Methanol