Journal article
Photolysis of Trenbolone Acetate Metabolites in the Presence of Nucleophiles: Evidence for Metastable Photoaddition Products and Reversible Associations with Dissolved Organic Matter
Environmental science & technology, Vol.54(19), pp.12181-12190
10/06/2020
DOI: 10.1021/acs.est.0c03821
PMID: 32910850
Abstract
Photolysis of trenbolone acetate (TBA) metabolites in the presence of various nitrogen-, sulfur-, or oxygen-containing nucleophiles (e.g., azide, ammonia, or thiosulfate, respectively) results in rapid (half-lives ∼20–60 min), photochemically induced nucleophile incorporation across the parent steroid’s trienone moiety. The formation of such nucleophile adducts limits formation of photohydrates, suggesting competition between the nucleophile and water for photochemical addition into the activated steroid structure. Analogous to previously reported photohydration outcomes, LC/MS analyses suggest that such photonucleophilic addition reactions are reversible, with more rapid elimination rates than thermal dehydration of photohydrates, and regenerate parent steroid structures. Beyond photonucleophilic addition pathways, we also found that hydroxylamine and presumed nucleophilic moieties in model dissolved organic matter (DOM; Fluka humic acid) can react via thermal substitution with TBA metabolite photohydrates, although this reaction with model DOM was only observed for photohydrates of trendione. Most nucleophile addition products [i.e., formed via (photo)reaction with thiosulfate, hydroxylamine, and ammonia] are notably more polar relative to the parent metabolite and photohydration products. Thus, if present, both nucleophilic adducts and bound residues in organic matter will facilitate transport and help mask detection of TBA metabolites in surface waters and treatment systems.
Details
- Title: Subtitle
- Photolysis of Trenbolone Acetate Metabolites in the Presence of Nucleophiles: Evidence for Metastable Photoaddition Products and Reversible Associations with Dissolved Organic Matter
- Creators
- Nicholas C Pflug - Department of ChemistryAndrew K Kral - University of IowaMadeline K Hankard - Department of ChemistryKathryn C Breuckman - Department of ChemistryEdward P Kolodziej - University of WashingtonJames B Gloer - Department of ChemistryKristine H Wammer - Department of ChemistryDavid M Cwiertny - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Environmental science & technology, Vol.54(19), pp.12181-12190
- Publisher
- American Chemical Society
- DOI
- 10.1021/acs.est.0c03821
- PMID
- 32910850
- ISSN
- 0013-936X
- eISSN
- 1520-5851
- Grant note
- DOI: 10.13039/100000165, name: Division of Chemistry, award: CHE-1608464, CHE-1609791; DOI: 10.13039/100008893, name: University of Iowa; DOI: 10.13039/100009768, name: University of St. Thomas; DOI: 10.13039/100000146, name: Division of Chemical, Bioengineering, Environmental, and Transport Systems, award: CBET-1335711
- Language
- English
- Date published
- 10/06/2020
- Academic Unit
- Center for Health Effects of Environmental Contamination; Civil and Environmental Engineering; Public Policy Center (Archive); Chemistry; Chemical and Biochemical Engineering
- Record Identifier
- 9984066352502771
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