Phosphatidylcholines with sn-1 saturated and sn-2 cis-monounsaturated acyl chains. Their melting behavior and structures.
Recently, we have shown by high resolution differential scanning calorimetry that the position of a cis double bond (delta-bond) in a series of 1-stearoyl-2-octadecenoyl- phosphatidylcholines can affect the phase transition temperature (Tm) or enthalpy (delta H) of the gel-to-liquid crystalline phase transition of this series of lipids in the following manner. The value of Tm (or delta H) is minimal when the delta-bond is positioned at C(11) in the sn-2 acyl chain; in addition, this value increases steadily as the delta-bond migrates toward either end of the acyl chain, resulting in a symmetrical, inverted bell-shaped profile (Wang, Z.-q., Lin, H.-n., Li, S., and Huang, C. (1995) J. Biol. Chem. 270, 2014-2023). In this communication, we have further demonstrated the inverted bell-shaped profile of Tm using 1-arachidoyl-2-eicosenoyl-phosphatidylcholines. In addition, we have extended the lipid series of 1-stearoyl-2-octadecenoyl-phosphatidylcholines to include 1-arachidoyl-2-octadecenoyl- phosphatidylcholines and 1-behenoyl-2-octadecenoyl-phosphatidylcholine, each series with a delta-bond at varying carbon position of 6, 7, 9, 11, 12, and 13. Calorimetric results obtained with these three series of lipids indicate that the inverted bell-shaped curve shifts toward higher temperatures in a nonuniform manner as the saturated sn-1 acyl chain length increases from 17 to 19 and then to 21 C-C bond lengths. Specifically, the Tm (or delta H) values are nearly identical for these cis-monoenoic lipids when their delta-bonds are positioned at C(13). Based on the height of the rotational energy barrier obtained with molecular mechanics calculations, it is evident that the rotational flexibility of the single C-C bond adjacent to the delta-bond in 1-stearoyl-2-octadecenoyl-phosphatidylcholine increases as the delta-bond migrates from C(9) to C(13). The differential scanning calorimetry results obtained with the three series of lipids can thus be attributed to an increase in the rotational flexibility of the short chain segment succeeding the C(14) atom in the sn-2 octadecenoyl chain. In this communication, we also propose that in the gel-state bilayer of sn-1 saturated/sn-2 cis-monounsaturated phosphatidylcholine the entire length of the shorter segment of the sn-2 acyl chain acts as a structural perturbing element; hence, it is mainly responsible for the large lower Tm of the monoenoic lipid relative to the saturated counterpart. Finally, two general equations relating Tm with the structural parameters of cis-monoenoic phosphatidylcholines are presented.(ABSTRACT TRUNCATED AT 400 WORDS)
Wang
G
G
Department of Biochemistry, University of Virginia, Charlottesville 22908, USA.
Lin
H N
HN
Li
S
S
Huang
C H
CH
D002152:Calorimetry, Differential Scanning; D005229:Fatty Acids, Monounsaturated; D008968:Molecular Conformation; D019301:Oleic Acid; D009829:Oleic Acids; D010713:Phosphatidylcholines / Q000737:chemistry*; D013229:Stearic Acids; D013329:Structure-Activity Relationship; D013816:Thermodynamics
D005229:Fatty Acids, Monounsaturated; D009829:Oleic Acids; D010713:Phosphatidylcholines; D013229:Stearic Acids; D019301:Oleic Acid; C031183:stearic acid