Analysis of organophosphate-Zn metalloporphyrin interactions via UV-vis spectroscopy and molecular modeling.

UV-vis absorption spectra of zinc tetraphenylporphine (ZnTPP) on interaction with six organophosphorus (OP) compounds in cyclohexane were compared using ab initio methods and the molecular and solvation ligand descriptors π(*), Vx, and σ. OPs with polarizable hydrocarbon substituents in the homologous series tri-ethyl, -pentyl, -octyl, and -phenyl phosphates and the toxicologically relevant methyl paraoxon (1a-e) each gave a red shift in the Soret band (λsor) of ZnTPP in the range of 8-10 nm. Sensitivity as ΔAsor-b/Δug OP for the spectral band of the ligand bound ZnTPP (λsor-b) decreased with increasing extent of alkyl and aromatic substitution. Calculated and combined energies for OP and ZnTPP examined as a function of distance (Å) between ligand and porphyrin center suggest increased steric crowding with increasing Vx, and aromatic content of the OP. Spectrally fitted K1:1 and ΔAsor-b/ug OP each vary exponentially with Vx/σ. Lack of a red shift in λsor-b where ZnTPP was titrated with the toxic diethyl chlorophosphate (1g) is consistent with a model in which the magnitude of ΔEsor is proportional to the donor capacity of the phosphoryl-O ligand.

Quantification of 2,4-D on solid-phase exposure sampling media by LC-MS-MS.

Three types of solid-phase chemical exposure sampling media: cellulose, polyurethane foam, and XAD-2, were analyzed for 2,4-dichlorophenoxyacetic acid (2,4-D) and the amine salts of 2,4-D. Individual samples were extracted into acidified methanol, and the extracts were analyzed via liquid chromatography-tandem mass spectrometry using electrospray ionization and a C(8) reversed-phase LC column. (13)C 2,4-D and a labeled benzoic acid (13)C or d5) were employed as the surrogate and internal standard, respectively. Over a three-year study of pesticide exposure among agricultural workers involving a high volume of analyses, values of average % recovery for (13)C 2,4-D on personal exposure samples ranged from 87 to 98 with a % relative standard deviation ranging from 7 to 12. The performance of the method compares favorably with that of the current National Institute for Occupational Safety and Health-recommended approach for the analysis of 2,4-D on these types of exposure sampling matrices.