On the Products of Cholesterol Autoxidation in Phospholipid Bilayers and the Formation of Secosterols Derived Therefrom
| Autor: | Nadia Zopyrus, Emily L. Schaefer, Zosia A. M. Zielinski, Glenn A. Facey, Derek A. Pratt |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
medicine.medical_treatment
Phospholipid 010402 general chemistry 01 natural sciences Catalysis chemistry.chemical_compound 03 medical and health sciences medicine Organic chemistry Humans Fragmentation (cell biology) Derivatization Phospholipids 030304 developmental biology 0303 health sciences Autoxidation 010405 organic chemistry Vitamin E General Chemistry General Medicine Product distribution 0104 chemical sciences Cholesterol chemistry Yield (chemistry) Epimer Oxidation-Reduction |
| Zdroj: | Angewandte Chemie. 132:2105-2110 |
| ISSN: | 1521-3757 0044-8249 |
| DOI: | 10.1002/ange.201914637 |
| Popis: | In homogenous solution, cholesterol autoxidation leads to a mixture of epimers of 5 primary products, whose concentrations vary in the presence/absence of antioxidants, such as vitamin E. Two of the products (5α-OOH and 6β-OOH) undergo Hock fragmentation to yield electrophilic secosterols implicated in disease. Herein, we show that the product distribution is similar in phospholipid bilayers, in that the 7-OOHs are the major products, but the presence/absence of vitamin E has no effect on the distribution. Cholesterol 7α-OOH, but not 7β-OOH, undergoes Hock fragmentation to yield a mixture of unprecedented A-ring cleavage products and 6,7-epoxides. When subjected to typical derivatization conditions, 7α-OOH yields products with essentially indistinguishable chromatographic and spectroscopic features from the previously identified secosterols, casting further doubt on their controversial origin from endogenous O3 . |
| Databáze: | OpenAIRE |
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