The role of excluded volume and electrostatics from coarse-grain modeling of the interaction of gemini surfactants with like-charged membranes

Abstract

Cationic systems composed of lipids and/or surfactants are of paramount importance in a variety of applications. Within these, gemini have attracted particular attention, mainly due to their improved aggregation properties and to the possibility of tuning offered by the presence of a spacer. In this work, a Monte Carlo simulation study with a coarse-grained model was employed to assess the interaction of cationic gemini surfactants with a like-charged model membrane. Separating the contribution of the excluded volume and that of the electrostatic effects in the organization of gemini–lipid membranes was the first goal of this work and the role of these factors was assessed varying the concentration, the spacer length and the headgroup charge of gemini surfactants. The results provide a new insight on the organization of lipid headgroups in the vicinity of gemini surfactants. It was found that the surfactant–lipid interaction is strongly affected by the surfactant spacer length, being controlled by an overall balance between excluded volume and surfactant–lipid and surfactant–surfactant electrostatic effects. It is also seen that the out-of-plane motion of the spacer has a significant effect upon membrane organization and counterion condensation. Good agreement was found with results previously obtained from atomistic simulation.

Keywords:

• dicationic gemini surfactant
• model membrane
• coarse-grained
• electrostatics
• excluded volume

Acknowledgements

This work was supported by FEDER funds through the COMPETE program – Programa Operacional Factores de Competitividade – and by National funds through Fundação para a Ciência e Tecnologia (FCT) under the Project PTDC/QUI-QUI/101442/2008 (COMPETE:FCOMP-01-0124-FEDER-010831). S.C.C.N. and J.A.S.A. gratefully acknowledge the post-doctoral research grants SFRH/BPD/71683/2010 and SFRH/BPD/82125/2011, respectively, and R.S.D. acknowledges the program Ciência 2007, all assigned by the Fundação para a Ciência e Tecnologia (FCT).