Phospholipids chiral at phosphorus. Properties of small unilamellar vesicles of chiral thiophosphatidylcholine

Abstract

The recent observation of the differences in the biophysical properties between 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and the Rp, Sp, and Rp + Sp isomers of 1,2-dipalmitoyl-sn-glycero-3-thiophosphocholine (DPPsC) in the multilamellar phase [Tsai, M.-D., Jiang, R.-T., & Bruzik, K. (1983) J. Am. Chem. Soc. 105, 2478-2480] prompted us to investigate the biophysical properties of the small unilamellar vesicles (SUV) of the above phospholipids. It was found that DPPC and DPPsC isomers showed approximately the same critical micelle concentrations and formed spherical SUV upon injection of their ethanolic solutions into an aqueous solution. However, the average sizes of the SUV of DPPsC isomers were significantly greater than that of DPPC prepared under the same conditions, as shown by their electron micrographs. The results of both 31P NMR line widths and the ratios of the entrapped solute to the total phospholipids further supported the following order in the average radius of the SUV: (Sp)-DPPsC greater than (Rp + Sp)-DPPsC greater than (Rp)-DPPsC greater than DPPC. Complete lysis of the SUV by melittin was demonstrated in all four cases. The DPPsC isomers showed gel-liquid-crystal transition temperatures of 43.8 +/- 0.1 degrees C, which are considerably higher than that of DPPC (37.9 degrees C) under the same conditions. In the SUV of an equimolar mixture of DPPC and (Rp + Sp)-DPPsC, DPPsC preferred to stay in the inner layer on the basis of 31P NMR studies by use of a shift reagent PrCl3.(ABSTRACT TRUNCATED AT 250 WORDS)