Effect of Alkyl Chain Length on Translocation of Rhodamine B n-Alkyl Esters across Lipid Membranes

Voltage-dependent translocation of a series of cationic rhodamine B derivatives differing in n-alkyl chain length (ethyl, butyl, octyl, dodecyl, octadecyl) from one lipid monolayer to another was studied by measuring electrical current relaxation after a voltage jump on a planar bilayer phosphatidylcholine (PC) membrane. The rate of the translocation decreased in the following series of lipids: diphytanyl-PC > dioleyl-PC > diphytanoyl-PC > dierucoyl-PC. For all the lipids studied, the rate increased with lengthening of the hydrocarbon chain of the rhodamine derivatives, with the increase being most pronounced for the compounds having a short alkyl chain. The results could be well explained by involvement of molecule reorientations in the process of transmembrane flip-flop of the hydrophobic membrane-bound compounds. However, an impact of membrane dipole potential on the translocation rate could not be excluded, because the dipole potential could contribute to the energy barrier for translocation of the compounds located at different depths in the water-membrane interface. Based on the data obtained, a difference in the dipole potential of ester diphytanoyl-PC membranes with respect to ether diphytanyl-PC was estimated to be 108 mV, highlighting the contribution of a layer of oriented carbonyl groups of the lipids to the membrane dipole potential.