Small angle X-ray scattering (SAXS),
electrospray ionization charge
detection mass spectrometry (CD-MS), dynamic light scattering (DLS),
and transmission electron microscopy (TEM) are used to characterize
poly(glycerol monomethacrylate)55-poly(2-hydroxypropyl
methacrylate)x (G55-Hx) vesicles prepared by polymerization-induced self-assembly
(PISA) using a reversible addition–fragmentation chain transfer
(RAFT) aqueous dispersion polymerization formulation. A G55 chain transfer agent is utilized to prepare a series of G55-Hx diblock copolymers, where the mean
degree of polymerization (DP) of the membrane-forming block (x) is varied from 200 to 2000. TEM confirms that vesicles
with progressively thicker membranes are produced for x = 200–1000, while SAXS indicates a gradual reduction in mean
aggregation number for higher x values, which is
consistent with CD-MS studies. Both DLS and SAXS studies indicate
minimal change in the overall vesicle diameter between x = 400 and 800. Fitting SAXS patterns to a vesicle model enables
calculation of the membrane thickness, degree of hydration of the
membrane, and the mean vesicle aggregation number. The membrane thickness
increases at higher x values, hence the vesicle lumen
must become smaller if the external vesicle dimensions remain constant.
Geometric considerations indicate that this growth mechanism lowers
the total vesicle interfacial area and hence reduces the free energy
of the system. However, it also inevitably leads to gradual ingress
of the encapsulated water molecules into the vesicle membrane, as
confirmed by SAXS analysis. Ultimately, the highly plasticized membranes
become insufficiently hydrophobic to stabilize the vesicle morphology
when x exceeds 1000, thus this PISA growth mechanism
ultimately leads to vesicle “death”.
The present paper describes the successful onepot synthesis of self-stabilized particles composed of amphiphilic block copolymers based on poly(methacrylic acid) (PMAA) obtained by polymerization-induced selfassembly. First, controlled radical polymerization of MAA is performed in water using the RAFT process by taking advantage of our recent results showing the successful RAFT polymerization of MAA in water [Chaduc et al. Macromolecules 2012, 45, 1241−1247. The so-formed hydrophilic macro-RAFT agents are then chain-extended in situ with a hydrophobic monomer to form amphiphilic block copolymer chains of controlled molar mass that self-assemble into stable nanoparticles. Various parameters such as the pH, the molar mass and the concentration of the PMAA segments or the nature of the hydrophobic block have been investigated.
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