Self-Assembly, Interfacial Properties, Interactions with Macromolecules and Molecular Modelling and Simulation of Microbial Bio-based Amphiphiles (Biosurfactants). A Tutorial Review

TL;DR

This tutorial review comprehensively examines microbial biosurfactants' self-assembly, interfacial behavior, and interactions with macromolecules, highlighting their potential as environmentally friendly alternatives to chemical surfactants.

Contribution

It provides an in-depth analysis of biosurfactants' properties, phase behavior, and interactions, integrating experimental data and molecular modeling insights, which advances understanding of their applications.

Findings

Biosurfactants exhibit unique self-assembly and phase behavior in water.

Their interfacial properties are critical for applications like emulsification and nanoparticle stabilization.

Molecular modeling helps elucidate their self-assembly mechanisms.

Abstract

Chemical surfactants are omnipresent in consumers' products but they suffer from environmental concerns. For this reason, complete replacement of petrochemical surfactants by biosurfactants constitute a holy grail but this is far from occurring any soon. If the "biosurfactants revolution" has not occurred, yet, mainly due to the higher cost and lower availability of biosurfactants, another reason explains this fact: the poor knowledge of their properties in solution. This tutorial review aims at reviewing the self-assembly properties and phase behavior, experimental (sections 2.3 and 2.4) and from molecular modelling (section 5), in water of the most important microbial biosurfactants (sophorolipids, rhamnolipids, surfacting, cellobioselipids, glucolipids) as well as their major derivatives. A critical discussion of such properties in light of the well-known packing parameter of surfactants is also provided (section 2.5). The relationship between the nanoscale self-assembly and macroscopic materials properties, including hydrogelling, solid foaming, templating or encapsulation is specifically discussed (section 2.7). We also present their self-assembly and adsorption at flat and complex air/liquid (e.g., foams), air/solid (adhesion), liquid/solid (nanoparticles) and liquid/liquid (e.g., emulsions) interfaces (section 3). A critical discussion on the use of biosurfactants as capping agents for the development of stable nanoparticles is specifically provided (section 3.2.4). Finally, we discuss the major findings involving biosurfactants and macromolecules, including proteins, enzymes, polymers and polyelectrolytes.