Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol

Cholesta-5,7,9(11)-trien-3β-ol (9,11-dehydroprovitamin D<sub>3</sub>, CTL) is used as a fluorescent probe to track the presence and migration of cholesterol in vivo. We recently described the photochemistry and photophysics of CTL in degassed and air-saturated tetrahydrofuran (THF) solut...

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Main Authors: Jack Saltiel, Sumesh B. Krishnan, Shipra Gupta, Anjan Chakraborty, Edwin F. Hilinski, Xinsong Lin
Format: Article
Language:English
Published: MDPI AG 2023-05-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/28/10/4086
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author Jack Saltiel
Sumesh B. Krishnan
Shipra Gupta
Anjan Chakraborty
Edwin F. Hilinski
Xinsong Lin
author_facet Jack Saltiel
Sumesh B. Krishnan
Shipra Gupta
Anjan Chakraborty
Edwin F. Hilinski
Xinsong Lin
author_sort Jack Saltiel
collection DOAJ
description Cholesta-5,7,9(11)-trien-3β-ol (9,11-dehydroprovitamin D<sub>3</sub>, CTL) is used as a fluorescent probe to track the presence and migration of cholesterol in vivo. We recently described the photochemistry and photophysics of CTL in degassed and air-saturated tetrahydrofuran (THF) solution, an aprotic solvent. The zwitterionic nature of the singlet excited state, <sup>1</sup>CTL* is revealed in ethanol, a protic solvent. In ethanol, the products observed in THF are accompanied by ether photoadducts and by photoreduction of the triene moiety to four dienes, including provitamin D<sub>3</sub>. The major diene retains the conjugated <i>s</i>-<i>trans</i>-diene chromophore and the minor is unconjugated, involving 1,4-addition of H at the 7 and 11 positions. In the presence of air, peroxide formation is a major reaction channel as in THF. X-ray crystallography confirmed the identification of two of the new diene products as well as of a peroxide rearrangement product.
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spelling doaj.art-84dedb4c99c14b059aace2caf48b95a42023-11-18T02:39:02ZengMDPI AGMolecules1420-30492023-05-012810408610.3390/molecules28104086Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in EthanolJack Saltiel0Sumesh B. Krishnan1Shipra Gupta2Anjan Chakraborty3Edwin F. Hilinski4Xinsong Lin5Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USADepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USADepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USADepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USADepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USADepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USACholesta-5,7,9(11)-trien-3β-ol (9,11-dehydroprovitamin D<sub>3</sub>, CTL) is used as a fluorescent probe to track the presence and migration of cholesterol in vivo. We recently described the photochemistry and photophysics of CTL in degassed and air-saturated tetrahydrofuran (THF) solution, an aprotic solvent. The zwitterionic nature of the singlet excited state, <sup>1</sup>CTL* is revealed in ethanol, a protic solvent. In ethanol, the products observed in THF are accompanied by ether photoadducts and by photoreduction of the triene moiety to four dienes, including provitamin D<sub>3</sub>. The major diene retains the conjugated <i>s</i>-<i>trans</i>-diene chromophore and the minor is unconjugated, involving 1,4-addition of H at the 7 and 11 positions. In the presence of air, peroxide formation is a major reaction channel as in THF. X-ray crystallography confirmed the identification of two of the new diene products as well as of a peroxide rearrangement product.https://www.mdpi.com/1420-3049/28/10/4086cholestatrienolphotochemistryphotophysicsfluorescence probe
spellingShingle Jack Saltiel
Sumesh B. Krishnan
Shipra Gupta
Anjan Chakraborty
Edwin F. Hilinski
Xinsong Lin
Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol
Molecules
cholestatrienol
photochemistry
photophysics
fluorescence probe
title Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol
title_full Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol
title_fullStr Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol
title_full_unstemmed Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol
title_short Photochemistry and Photophysics of Cholesta-5,7,9(11)-trien-3β-ol in Ethanol
title_sort photochemistry and photophysics of cholesta 5 7 9 11 trien 3β ol in ethanol
topic cholestatrienol
photochemistry
photophysics
fluorescence probe
url https://www.mdpi.com/1420-3049/28/10/4086
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