Thermodynamic Analysis of Chain-Melting Transition Temperatures for Monounsaturated Phospholipid Membranes: Dependence on cis-Monoenoic Double Bond Position

AbstractUnsaturated phospholipid is the membrane component that is essential to the dynamic environment needed for biomembrane function. The dependence of the chain-melting transition temperature, Tt, of phospholipid bilayer membranes on the position, nu, of the cis double bond in the glycerophospholipid sn-2 chain can be described by an expression of the form Tt=Ttc(1+h′c|nu−nc|)/(1+s′c|nu−nc|), where nc is the chain position of the double bond corresponding to the minimum transition temperature, Ttc, for constant diacyl lipid chain lengths. This implies that the incremental transition enthalpy (and entropy) contributed by the sn-2 chain is greater for whichever of the chain segments, above or below the double-bond position, is the longer. The critical position, nc, of the double bond is offset from the center of the sn-2 chain by an approximately constant amount, δnc ≈ 1.5 C-atom units. The dependence of the parameters Ttc, h′c, and s′c on sn-1 and sn-2 chain lengths can be interpreted consistently when allowance is made for the chain packing mismatch between the sn-1 and sn-2 chains. The length of the sn-2 chain is reduced by ∼0.8 C-atom units by the cis double bond, in addition to a shortening by ∼1.3 C-atom units by the bent configuration at the C-2 position. Based on this analysis, a general thermodynamic expression is proposed for the dependence of the chain-melting transition temperature on the position of the cis double bond and on the sn-1 and sn-2 chain lengths. The above treatment is restricted mostly to double-bond positions close to the center of the sn-2 chain. For double bonds positioned closer to the carboxyl or terminal methyl ends of the sn-2 chain, the effects on transition enthalpy can be considerably larger. They may be interpreted by the same formalism, but with different characteristic parameters, h′c and s′c, such that the shorter of the chain segments makes a considerably smaller contribution to the calorimetric properties of the chain-melting transition