Role of the cholesterol hydroxyl group in the chemical exchange saturation transfer signal at -1.6 ppm.


Journal

NMR in biomedicine
ISSN: 1099-1492
Titre abrégé: NMR Biomed
Pays: England
ID NLM: 8915233

Informations de publication

Date de publication:
09 2020
Historique:
received: 05 04 2020
revised: 10 05 2020
accepted: 29 05 2020
pubmed: 24 6 2020
medline: 8 10 2021
entrez: 24 6 2020
Statut: ppublish

Résumé

Chemical exchange saturation transfer (CEST) can provide metabolite-weighted images in the clinical setting; therefore, understanding the origin of each CEST signal is essential to revealing the changes in diseases at the molecular level, which would provide further insight for diagnoses and treatments. The CEST signal at -1.6 ppm is attributed to the choline methyl group of phosphatidylcholines. The methyl groups have no exchangeable protons, so the corresponding CEST signals must result from the relayed nuclear Overhauser effect (rNOE); however, the detailed mechanism remains unclear. Cholesterol is a major component of biological membranes, and its content is closely related to the dynamics and phases of these lipids. However, cholesterol has a hydroxyl group, which could participate in proton exchange to complete the rNOE process. In this study, we used liposomes containing cholesterol and its analogs (5α-cholestane and progesterone), which presumably have similar capabilities of influencing lipid bilayers, and found that the steroid hydroxyl group is the key to inducing the rNOE at -1.6 ppm. Our results suggest that the origin of the rNOE at -1.6 ppm likely requires an intermolecular NOE between the proton of the choline methyl group and that of the cholesterol hydroxyl group, and a chemical exchange between the cholesterol hydroxyl group and bulk water. However, the phenomenon in which the rNOE at -1.6 ppm appears when the cholesterol concentration is high seems to contradict the in vivo results, suggesting a more complicated mechanism associated with the rNOE at -1.6 ppm in biological membranes.

Identifiants

pubmed: 32575161
doi: 10.1002/nbm.4356
doi:

Substances chimiques

Cholestanes 0
Liposomes 0
1,2-Dipalmitoylphosphatidylcholine 2644-64-6
Palmitic Acid 2V16EO95H1
Cholesterol 97C5T2UQ7J

Types de publication

Journal Article Research Support, Non-U.S. Gov't

Langues

eng

Sous-ensembles de citation

IM

Pagination

e4356

Informations de copyright

© 2020 John Wiley & Sons, Ltd.

Références

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Auteurs

Yu-Chi Chang (YC)

Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi, Taiwan.

Hong-Qing Liu (HQ)

Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi, Taiwan.

Jung-Hsuan Chang (JH)

Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi, Taiwan.

Yu-Yen Chang (YY)

Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi, Taiwan.

Eugene C Lin (EC)

Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi, Taiwan.

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