Multicompartment Polymeric Micelles Based on Hydrocarbon and Fluorocarbon Polymerizable Surfactants

Abstract

The synthesis of multicompartment polymeric micelles (MCPMs) has been achieved by aqueous radical terpolymerization of a water-soluble monomer (acrylamide) with both hydrocarbon (H) and fluorocarbon (F) surfactants (surfmers) in the micellar state. The selected H- and F-surfmers are CH2CHCON(C2H5)CH2CH2N(CH3)2CH2COOC16H33/Br/Cl (HS6) and CH2CHCONHCH2CH2N(CH3)2CH2COOCH2CH2C8F17/Br (FS3), respectively. Their mutual incompatibility in aqueous solution has been checked by conductivity and surface tension experiments. Two cmc values are found, in favor of the coexistence of two distinct types of micelles at surfactant concentrations above 1 mmol/L (second cmc) over a broad composition range. The solubilization properties of the pure and mixed surfactant systems have been studied for different hydrophobic probes. Significant differences in the solubilization capacity occur due to the nature of the dye, of the surfactant, and of the micelle shape and composition. A kinetic study on the incorporation behavior of the H- and F-surfmers in the polyacrylamide backbone during a batch polymerization shows a compositional drift as a function of conversion which is attributed to micellar effects. A semicontinuous process has been designed which allows the correction for this compositional drift. The presence of well-segregated H- and F-microdomains in terpolymers could be inferred from viscosity and fluorescence experiments. Furthermore, the solubilization of decalin is enhanced in terpolymer solutions with respect to that of copolymer solutions. This was attributed to the formation of larger hydrocarbon cores in the former case due to repulsive H/F interactions in the polymeric chains.

Perfluorocarbons: Life sciences and biomedical uses Dedicated to the memory of Professor Guy Ourisson, a true RENAISSANCE man.

“…''Multicompartment micelles'' 25 have, for example, been prepared by micellar terpolymerization of acrylamide with both hydrocarbon-and fluorocarbon-polymerizable surfactants. 26 Other multicompartmented systems have been obtained by self-assembly in water of linear 27 or star-shaped [ Fig. 3(a)] 28 triblock copolymers bearing a highly fluorinated arm, a polystyrene arm, and a polymorpholinium or poly(ethylene oxide) arm.…”

Understanding Multicompartment Micelles Using Dissipative Particle Dynamics Simulation

“…[15][16][17][18][19][20] At the moment, most work has focused on the preparation and characterization of new multicompartment micelles, [21][22][23][24][25] and an initial effort on the storage of two agents in a multicompartment micelle has recently been made. [26] Due to their structural complexity, it is difficult to assess the structure of the core of a multicompartment micelle rigorously, or indeed to visualize the evolution process of a multicompartment micelle directly by experiment.…”

“…To date, various preparation strategies have been developed. For example, Candau and co-workers [15] synthesized multicompartment micelles through aqueous radical terpolymerization of a water soluble monomer (acrylamide) with both hydrocarbon (H) and fluorocarbon (F) surfactants (surfmers) in the micellar state. They also investigated different ways to improve the incompatibility between H-and F-surfmers and described a semi-continuous polymerization process developed for the terpolymerization of demixed fluorocarbon and hydrocarbon micelles with acrylamide.…”

Preparation of polymeric nanoparticles using a new polymerizable surfactant

“…In recent years much attention has been devoted to synthesizing polymerizable surfactants, so-called surfmers (surface active substances having an interfacial activity and bearing reactive groups) [6], and to use them [7,8] as potential building blocks for nanocarriers of active substances [9]. The polymerization process of the micellized polymerizable surfactant (having an interfacial activity and bearing reactive groups) may lead to stable polymeric micelles [10]. stable polymeric nanostructures in dispersion polymerizations is introduced.…”