Effects of Natural Rhamnolipid Mixture on Dioleoylphosphatidylcholine Model Membrane Depending on Method of Preparation and Sterol Content

Abstract

Rhamnolipids as biosurfactants have a potentially wide range of applications, for example, as “green” surfactants or components of drug delivery systems, which is associated with the features of their interaction with cell membranes. However, as noted in the literature, those kind of features have not been sufficiently studied now. This paper presents a study of the interaction of a natural mixture of rhamnolipids produced by bacteria of the rhizosphere zone of plants Pseudomonas aeruginosa with model membranes—liposomes based on dioleoylphosphatidylcholine (DOPC), depending on the method of their preparation and the content of sterols—ergosterol, cholesterol, lanosterol. Liposomes with rhamnolipids were prepared by two protocols: with film method from a mixture of DOPC and rhamnolipids; with film method from DOPC and injection of water solution of rhamnolipids. Joint analysis of the data of 31P NMR spectroscopy and ATR-FTIR spectroscopy showed that in the presence of rhamnolipids, the mobility of the head group of the DOPC phospholipid increases, the conformational disorder of the hydrophobic tail increases, and the degree of hydration of the C=O and P=O groups of the phospholipid decreases. It can be assumed that, when prepared from a mixture, rhamnolipids are incorporated into the membrane in the form of clusters and are located closer to the middle of the bilayer; while when prepared by injection, rhamnolipid molecules migrate into the membrane in the form of individual molecules and are located closer to the head part of phospholipids. The sterol composition of the model membrane also affects the interaction of rhamnolipids with the membrane. Here it is worth noting the possible presence of type of interaction between rhamnolipids and ergosterol differ from other investigated sterols, due to which rhamnolipid molecules are embedded in the area where ergosterol is located.