Photochemistry and photophysics of cholesta-5,7,9(11)-trien-3β-ol: a fluorescent analogue of cholesterol

• Published in: Photochemical & photobiological sciences 2022, Vol.21 (1), p.37-47
• Main Authors: Saltiel, Jack, Krishnan, Sumesh B., Gupta, Shipra, Hernberg, E. Aliea, Clark, Ronald J.
• Format: Article
• Language: English
• Subjects: Biochemistry; Biomaterials; Chemistry; Chemistry and Materials Science; Cholesterol; Crystallography, X-Ray; Magnetic Resonance Spectroscopy; Original Papers; Photochemistry; Physical Chemistry; Plant Sciences; Trientine
• ISSN: 1474-905X; 1474-9092
• DOI: 10.1007/s43630-021-00131-w

Cholesta-5,7,9(11)-trien-3β-ol (9,11-dehydroprovitamin D 3 , CTL) is used as a fluorescent probe to track the presence and migration of cholesterol in vivo. CTL is known to be photochemically active, but little consideration has been given to the formation efficiency and possible toxicity of its photoproducts. In degassed tetrahydrofuran (THF) solution, we isolated the photoproduct of CTL and of its 25-hydroxy derivative (HOCTL), and X-ray crystal structures were obtained for HOCTL and the photorearrangement product. The X-ray crystal structure and its 1 H NMR spectrum confirm the product structure as a pentacyclic HOCTL isomer. In the presence of air in THF, endoperoxide formation via [2+4] addition of 1 O 2 * across the B ring of CTL or HOCTL becomes the dominant photoreaction. The UV spectrum and decay kinetics of the triplet state of HOCTL, the precursor of 1 O 2 *, are determined by transient absorption spectroscopy. We confirm the proposed structure of the endoperoxide by X-ray crystallography. Kinetics analysis of quantum yields provides rate constants for photophysical and photochemical events. Graphical abstract