Physicochemical properties of pH-controlled polyion complex (PIC) micelles of poly(acrylic acid)-based double hydrophilic block copolymers and various polyamines |
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Authors: | J?Warnant N?Marcotte J?Reboul G?Layrac A?Aqil C?Jer?me Email author" target="_blank">D?A?LernerEmail author C?Gérardin |
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Institution: | 1.Institut Charles Gerhardt,UMR 5253 CNRS/ENSCM/UM2/UM1,Montpellier Cedex 5,France;2.Center for Education and Research on Macromolecules (CERM),University of Liège,Liège,Belgium |
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Abstract: | The physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted
of electrostatic complexes of two oppositely charged polyelectrolytes. The pH-sensitive micelles were obtained with double
hydrophilic block copolymers containing a poly(acrylic acid) block linked to a modified poly(ethylene oxide) block and various
polyamines (polylysine, linear and branched polyethyleneimine, polyvinylpyridine, and polyallylamine). The pH range of micellization
in which both components are ionized was determined for each polyamine. The resulting PIC micelles were characterized using
dynamic light scattering and small-angle X-ray scattering experiments (SAXS). The PIC micelles presented a core–corona nanostructure
with variable polymer density contrasts between the core and the corona, as revealed by the analysis of the SAXS curves. It
was shown that PIC micelle cores constituted by polyacrylate chains and polyamines were more or less dense depending on the
nature of the polyamine. It was also determined that the density of the cores of the PIC micelles depended strongly on the
nature of the polyamine. These homogeneous cores were surrounded by a large hairy corona of hydrated polyethylene oxide block
chains. Auramine O (AO) was successfully entrapped in the PIC micelles, and its fluorescence properties were used to get more
insight on the core properties. Fluorescence data confirmed that the cores of such micelles are quite compact and that their
microviscosity depended on the nature of the polyamine. The results obtained on these core–shell micelles allow contemplating
a wide range of applications in which the AO probe would be replaced by various cationic drugs or other similarly charged
species to form drug nanocarriers or new functional nanodevices. |
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