A f-19 and deuterium nmr-study of two novel fluorosterols and their properties in model membranes and high-density-lipoprotein

David G. Reid, L.K. MacLachlan, K.E. Suckling, A. Gee, S. Cresswell, C.J. Suckling

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Fluorine-19 nuclear magnetic resonance at 235 MHz has been used to characterize the NMR properties of two novel fluorinated sterols, 6,6-difluorocholestanol and 7,7-difluorocholestanol, and various 3-ester derivatives. F-19-F-19 and F-19-H-1 coupling constants in chloroform are reported. H-2-NMR studies of side-chain perdeuterated dimyristoylphosphatidylcholine (DMPC-d54) prove that the two unesterified fluorosterols affect model membrane dynamical properties in a manner analogous to cholesterol. In aqueous detergent the F-19 chemical shifts of both 6,6- and 7,7-difluorocholestanols are perturbed about 1 ppm upfield by esterification at the 3-position, suggesting that F-19-NMR may be a useful monitor of enzyme catalyzed sterol acylation in vitro. Finally 6,6-difluorocholestanol oleate has been incorporated into human high density lipoprotein (HDL) and its F-19 signals observed in this environment. The appearance of the spectrum, and the results of lipophilic relaxation probe experiments, indicate that the acyl sterol partitions into at least two environments, and exhibits slightly different chemical shift and homonuclear scalar coupling characteristics in each.
LanguageEnglish
Pages175-181
Number of pages6
JournalChemistry and Physics of Lipids
Volume58
Issue number1-2
Publication statusPublished - May 1991

Fingerprint

Deuterium
Sterols
HDL Lipoproteins
Dimyristoylphosphatidylcholine
Nuclear magnetic resonance
Membranes
Chemical shift
Acylation
Fluorine
Esterification
Oleic Acid
Chloroform
Detergents
Esters
Magnetic Resonance Spectroscopy
Cholesterol
Enzymes
Derivatives
6,6-difluorocholestanol
7,7-difluorocholestanol

Keywords

  • F-19-NMR
  • H-2-NMR
  • fluorosterols
  • HDL
  • DMPC-D54
  • nuclear magnetic resonance
  • cholesterol
  • metabolism
  • molecules

Cite this

Reid, David G. ; MacLachlan, L.K. ; Suckling, K.E. ; Gee, A. ; Cresswell, S. ; Suckling, C.J. / A f-19 and deuterium nmr-study of two novel fluorosterols and their properties in model membranes and high-density-lipoprotein. In: Chemistry and Physics of Lipids. 1991 ; Vol. 58, No. 1-2. pp. 175-181.
@article{f124bfe14cdf47e5895c12314dd646aa,
title = "A f-19 and deuterium nmr-study of two novel fluorosterols and their properties in model membranes and high-density-lipoprotein",
abstract = "Fluorine-19 nuclear magnetic resonance at 235 MHz has been used to characterize the NMR properties of two novel fluorinated sterols, 6,6-difluorocholestanol and 7,7-difluorocholestanol, and various 3-ester derivatives. F-19-F-19 and F-19-H-1 coupling constants in chloroform are reported. H-2-NMR studies of side-chain perdeuterated dimyristoylphosphatidylcholine (DMPC-d54) prove that the two unesterified fluorosterols affect model membrane dynamical properties in a manner analogous to cholesterol. In aqueous detergent the F-19 chemical shifts of both 6,6- and 7,7-difluorocholestanols are perturbed about 1 ppm upfield by esterification at the 3-position, suggesting that F-19-NMR may be a useful monitor of enzyme catalyzed sterol acylation in vitro. Finally 6,6-difluorocholestanol oleate has been incorporated into human high density lipoprotein (HDL) and its F-19 signals observed in this environment. The appearance of the spectrum, and the results of lipophilic relaxation probe experiments, indicate that the acyl sterol partitions into at least two environments, and exhibits slightly different chemical shift and homonuclear scalar coupling characteristics in each.",
keywords = "F-19-NMR, H-2-NMR, fluorosterols, HDL, DMPC-D54, nuclear magnetic resonance, cholesterol, metabolism, molecules",
author = "Reid, {David G.} and L.K. MacLachlan and K.E. Suckling and A. Gee and S. Cresswell and C.J. Suckling",
year = "1991",
month = "5",
language = "English",
volume = "58",
pages = "175--181",
journal = "Chemistry and Physics of Lipids",
issn = "0009-3084",
number = "1-2",

}

A f-19 and deuterium nmr-study of two novel fluorosterols and their properties in model membranes and high-density-lipoprotein. / Reid, David G.; MacLachlan, L.K.; Suckling, K.E.; Gee, A.; Cresswell, S.; Suckling, C.J.

In: Chemistry and Physics of Lipids, Vol. 58, No. 1-2, 05.1991, p. 175-181.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A f-19 and deuterium nmr-study of two novel fluorosterols and their properties in model membranes and high-density-lipoprotein

AU - Reid, David G.

AU - MacLachlan, L.K.

AU - Suckling, K.E.

AU - Gee, A.

AU - Cresswell, S.

AU - Suckling, C.J.

PY - 1991/5

Y1 - 1991/5

N2 - Fluorine-19 nuclear magnetic resonance at 235 MHz has been used to characterize the NMR properties of two novel fluorinated sterols, 6,6-difluorocholestanol and 7,7-difluorocholestanol, and various 3-ester derivatives. F-19-F-19 and F-19-H-1 coupling constants in chloroform are reported. H-2-NMR studies of side-chain perdeuterated dimyristoylphosphatidylcholine (DMPC-d54) prove that the two unesterified fluorosterols affect model membrane dynamical properties in a manner analogous to cholesterol. In aqueous detergent the F-19 chemical shifts of both 6,6- and 7,7-difluorocholestanols are perturbed about 1 ppm upfield by esterification at the 3-position, suggesting that F-19-NMR may be a useful monitor of enzyme catalyzed sterol acylation in vitro. Finally 6,6-difluorocholestanol oleate has been incorporated into human high density lipoprotein (HDL) and its F-19 signals observed in this environment. The appearance of the spectrum, and the results of lipophilic relaxation probe experiments, indicate that the acyl sterol partitions into at least two environments, and exhibits slightly different chemical shift and homonuclear scalar coupling characteristics in each.

AB - Fluorine-19 nuclear magnetic resonance at 235 MHz has been used to characterize the NMR properties of two novel fluorinated sterols, 6,6-difluorocholestanol and 7,7-difluorocholestanol, and various 3-ester derivatives. F-19-F-19 and F-19-H-1 coupling constants in chloroform are reported. H-2-NMR studies of side-chain perdeuterated dimyristoylphosphatidylcholine (DMPC-d54) prove that the two unesterified fluorosterols affect model membrane dynamical properties in a manner analogous to cholesterol. In aqueous detergent the F-19 chemical shifts of both 6,6- and 7,7-difluorocholestanols are perturbed about 1 ppm upfield by esterification at the 3-position, suggesting that F-19-NMR may be a useful monitor of enzyme catalyzed sterol acylation in vitro. Finally 6,6-difluorocholestanol oleate has been incorporated into human high density lipoprotein (HDL) and its F-19 signals observed in this environment. The appearance of the spectrum, and the results of lipophilic relaxation probe experiments, indicate that the acyl sterol partitions into at least two environments, and exhibits slightly different chemical shift and homonuclear scalar coupling characteristics in each.

KW - F-19-NMR

KW - H-2-NMR

KW - fluorosterols

KW - HDL

KW - DMPC-D54

KW - nuclear magnetic resonance

KW - cholesterol

KW - metabolism

KW - molecules

UR - http://www.chem.strath.ac.uk/people/academic/sarah_l_cresswell/publications

M3 - Article

VL - 58

SP - 175

EP - 181

JO - Chemistry and Physics of Lipids

T2 - Chemistry and Physics of Lipids

JF - Chemistry and Physics of Lipids

SN - 0009-3084

IS - 1-2

ER -