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Biophys J, August 2001, p. 969-982, Vol. 81, No. 2
*University of Leipzig, Institute of Medical Physics and
Biophysics, D-04103 Leipzig, Germany;
National Institutes
of Health, National Institute on Alcohol Abuse and Alcoholism,
Laboratory of Membrane Biochemistry and Biophysics, Rockville, Maryland
20852 USA
To gain a better understanding of the biological role of
polyunsaturated phospholipids, infrared (IR) linear dichroism, NMR, and
x-ray diffraction studies have been conducted on the lyotropic phase
behavior and bilayer dimensions of sn-1 chain
perdeuterated 1-stearoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine
(SDPC-d35), a mixed-chain saturated (18:0)-polyunsaturated (22:6
3)
lipid. SDPC films were hydrated at definite values of temperature (T) and relative humidity (RH). In excess water, the lipid forms
exclusively lamellar phases in the temperature range 0-50°C. Upon
dehydration the lipid undergoes the main phase transition between the
liquid-crystalline (L
) and gel (L
) phase
at T < 15°C. Both the saturated and polyunsaturated chains
adopt a stretched conformation in the L
phase,
presumably the all-trans (stearoyl) and angle iron or
helical (docosahexaenoyl) one. A new fluid lamellar phase
(L
') was found in partially hydrated samples at T > 15°C. SDPC membranes expand laterally and contract vertically in
the L
' phase when water was removed. This tendency is in
sharp contrast to typical dehydration-induced changes of membrane
dimensions. The slope of the phase transition lines in the RH-T phase
diagram reveal that the lyotropic L
'-L
and L
-L
transitions are driven by
enthalpy and entropy, respectively The possible molecular origin of the
phase transitions is discussed. The properties of SDPC are compared
with that of membranes of monounsaturated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine
(POPC-d31).
Biophys J, August 2001, p. 969-982, Vol. 81, No. 2
© 2001 by the Biophysical Society 0006-3495/01/08/969/14 $2.00
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