Lipid bilayer and water proton magnetization transfer: Effect of cholesterol

Magnetization transfer between macromolecules and water can be a significant factor contributing to tissue water 1H relaxation. Using saturation transfer techniques, the degree of magnetization transfer between the macromolecular matrix and bulk water 1H can be directly measured and magnetization transfer contrast (MTC) can be generated in MR images. A significant degree of MTC has been observed in tissues with high plasma membrane content such as kidney and brain. The purpose of this study was to establish whether lipid bilayers, as models for cell membranes, could exchange magnetization with the water solvent and whether this effect could contribute to MTC observed in intact tissues. Magnetization transfer was measured in aqueous dispersions of egg phosphatidylcholine (EPC) in the presence and absence of cholesterol. It was found that neither EPC bilayers nor cholesterol by themselves significantly exchanged magnetization with bulk water 1H. However, as the concentration of cholesterol was increased, the pseudo‐first‐order magnetization exchange rate increased to a maximum value of ∼1 s−1. The cholesterol‐induced 1H magnetization exchange may be related either to longer correlation times of the lipid or to an increase in the number of water molecules associated with the bilayer. These results indicate that EPC‐cholesterol bilayers exchange 1H magnetization with bulk water. These results are consistent with lipid bilayer contributions to bulk water relaxation and MTC in intact biological tissues. © 1991 Academic Press. Inc.

[1]  A. Blaurock,et al.  Lipid/myelin basic protein multilayers. A model for the cytoplasmic space in central nervous system myelin. , 1984, Journal of molecular biology.

[2]  S. Forsén,et al.  Study of Moderately Rapid Chemical Exchange Reactions by Means of Nuclear Magnetic Double Resonance , 1963 .

[3]  S. Chan,et al.  The phospholipid packing arrangement in small bilayer vesicles as revealed by proton magnetic resonance studies at 500 MHz. , 1982, Biochimica et biophysica acta.

[4]  A. D. Bain,et al.  A new way of measuring NMR spin-spin relaxation times (T2) , 1981 .

[5]  Robert S. Balaban,et al.  NMR imaging of labile proton exchange , 1990 .

[6]  V. Simplaceanu,et al.  Effects of cholesterol or gramicidin on slow and fast motions of phospholipids in oriented bilayers. , 1989, Proceedings of the National Academy of Sciences of the United States of America.

[7]  T. McIntosh,et al.  Cholesterol modifies the short-range repulsive interactions between phosphatidylcholine membranes. , 1989, Biochemistry.

[8]  S. H. Koenig,et al.  Magnetic cross-relaxation among protons in protein solutions. , 1978, Biochemistry.

[9]  E. Samulski,et al.  Cross relaxation and spin diffusion in the proton NMR of hydrated collagen , 1977, Nature.

[10]  C. P. Taylor,et al.  The influence of cholesterol on molecular motion in egg lecithin bilayers--a variable-frequency electron spin resonance study of a cholestane spin probe. , 1974, Archives of biochemistry and biophysics.

[11]  E A Dratz,et al.  Proton NMR T1, T2, and T1 rho relaxation studies of native and reconstituted sarcoplasmic reticulum and phospholipid vesicles. , 1982, Biophysical journal.

[12]  L. Vander Elst,et al.  Field-cycling relaxometry: medical applications. , 1988, Radiology.

[13]  I. Smith,et al.  High resolution deuterium magnetic resonance ‐ An approach to the study of molecular organization In biological membranes and model systems , 1973, FEBS letters.

[14]  D. Cafiso,et al.  Phospholipid packing and conformation in small vesicles revealed by two-dimensional 1H nuclear magnetic resonance cross-relaxation spectroscopy. , 1986, Biophysical journal.

[15]  R. Balaban,et al.  Magnetization transfer contrast (MTC) and tissue water proton relaxation in vivo , 1989, Magnetic resonance in medicine.

[16]  E. Samulski,et al.  The measurement of cross-relaxation effects in the proton NMR spin-lattice relaxation of water in biological systems: Hydrated collagen and muscle☆ , 1978 .

[17]  Modeling of proton spin relaxation in muscle tissue using nuclear magnetic resonance spin grouping and exchange analysis. , 1986, Biophysical journal.

[18]  Y Van Haverbeke,et al.  The uncommon longitudinal relaxation dispersion of human brain white matter , 1989, Magnetic resonance in medicine.

[19]  Seymour H. Koenig,et al.  The Dynamics of Water-Protein Interactions: Results from Measurements of Nuclear Magnetic Relaxation Dispersion , 1980 .

[20]  S. Forsén,et al.  Transient and Steady‐State Overhauser Experiments in the Investigation of Relaxation Processes. Analogies between Chemical Exchange and Relaxation , 1966 .

[21]  C. Huang,et al.  Structural studies on phophatidylcholine-cholesterol mixed vesicles. , 1975, Biochemistry.