The effects of lipid structure on the kinetics of spontaneous transfer of a series of phosphatidylcholines have been determined. Donors, which were model-reassembled high-density lipoproteins composed of apo A-I, 1-palmitoyl-2-oleoylphosphatidylcholine, and a trace of a radiolabeled lipid, were mixed with acceptors, which were human low-density lipoproteins. Within a series of phosphatidylcholines, the addition of double bonds and methylene units, respectively, increased and decreased the rate of transfer in a predictable way. An equation that predicts the rates of transfer of a large number of diacylglycerides and phosphoglycerides from any lipoprotein has been empirically derived from these data. The transfers of phosphatidylcholines that contain superpolyunsaturated fatty acids (four or more double bonds) do not obey the derived equation, probably due to limitations on the number of conformational degrees of freedom in these lipids. The range of measured transfer halftimes extends from less than 2 h to more than 12 days. Thus, the spontaneous transfer halftimes of some (but not all) lipids are short compared to the lifetime of lipoproteins in plasma. These results suggest that some lipids transfer among lipoproteins and cells via a spontaneous mechanism while others require specific transfer factors or hydrolysis to achieve this within a physiologically significant time frame.

Small amounts of dietary n-3 fatty acids can have dramatic physiological effects, including the reduction of plasma triglycerides and an elevation of cellular eicosapentanoic (EPA) and docosahexanoic acids (DHA) at the expense of arachidonic acid (AA). We investigated the effects of alterations in the fatty acid compositions of cardiac sarcoplasmic reticulum (CSR) produced by dietary manipulation on the calcium pump protein that is required for energy dependent calcium transport. CSR was isolated from rats fed menhaden oil, which is rich in n-3 fatty acids, and from control animals that were given corn oil. Relative to control membranes, those isolated from rats fed menhaden oil, had a lower content of saturated phospholipids, an increased DHA/AA ratio, and an increased ratio of n-3 to n-6 fatty acids. These changes were associated with a 30% decrease in oxalate-facilitated, ATP-dependent calcium uptake and concomitant decreased Ca-ATPase activity in the membranes from the animals fed menhaden oil. In contrast, there was no alteration in active pump sites as measured by phosphoenzyme formation. Thus, the CSR Ca-ATPase function can be altered by dietary interventions that change the composition, and possibly structure, of the phospholipid membranes thereby affecting enzyme turnover.