Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring‐opening polymerization of ε‐caprolactone substituted by various functional groups, protected if needed, in α‐ or γ‐position. In a second strategy, the functional groups are grafted onto preformed polyesters chains in α‐position of the carbonyl groups. α‐chloro‐ε‐caprolactone is quite an interesting monomer because, after polymerization, the activated chloride can be easily derivatized by atom transfer radical addition and “click” chemistry, respectively. Similarly, γ‐acrylic‐ε‐caprolactone is precursor of (co)polyesters well‐suited to derivatization of the pendent double bonds by Michael addition.

The Michael-type addition of aliphatic (co)polyesters onto gamma-acryloyloxy epsilon-caprolactone units is a very straightforward technique of functionalization and grafting, which is tolerant to a variety of functional groups and does not require intermediate protection/deprotection steps.

Well‐defined copolymers of biocompatible poly(ϵ‐caprolactone) (PCL) and poly(ethylene oxide) (PEO) are synthesized by two methods. Graft copolymers with a gradient structure are prepared by ring‐opening copolymerization of ϵ‐caprolactone (ϵCL) with a PEO macromonomer of the ϵCL‐type. The ϵCL polymerization is initiated by a PEO macroinitiator to prepare diblock copolymers. These amphiphilic copolymers are used as stabilizers for biodegradable poly(D,L‐lactide) (PLA) nanoparticles prepared by a nanoprecipitation technique. The effect of the copolymer characteristic features (architecture, composition, and amount) on the nanoparticle formation and structure is investigated. The average size, size distribution, and stability of aqueous suspensions of the nanoparticles is measured by dynamic light scattering. For comparison, an amphiphilic random copolymer, poly(methyl methacrylate‐co‐methacrylic acid) (P(MMA‐co‐MA)), is synthesized. The stealthiness of the nanoparticles is analyzed in relation to the copolymer used as stabilizer. For this purpose, the activation of the complement system by nanoparticles is investigated in vitro using human serum. This activation is much less important whenever the nanoparticles are stabilized by a PEO‐containing copolymer rather than by the P(MMA‐co‐MA) amphiphile. The graft copolymers with a gradient structure and the diblock copolymers with similar macromolecular characteristics (molecular weight and hydrophilicity) are compared on the basis of their capacity to coat PLA nanoparticles and to make them stealthy.

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This work deals with the self-assembly in water of ABC miktoarm star terpolymers consisting of hydrophobic poly(-caprolactone), hydrophilic poly(ethylene oxide) (PEO), and pH-sensitive poly(2-vinylpyridine) (P2VP). A variety of experimental techniques were used, including dynamic light scattering, transmission electron microscopy, and zeta potential. Special attention was paid to the pH dependency of the supramolecular self-assemblies. A key observation is the capability of the miktoarm terpolymers to form micelles stable over the whole range of pH, although a transition was observed from neutral to highly positively charged nanoobjects upon decreasing pH.

In the present work, a method is proposed to assemble pH‐responsive, flower‐like micelles that can expose a targeting unit at their periphery upon a decrease in pH. The micelles are composed of a novel biotinylated triblock copolymer of poly(εε‐caprolactone)‐block‐poly(ethylene oxide)‐block‐poly(2‐vinylpyridine) (PCL‐b‐PEO‐b‐P2VP) and the non‐biotinylated analogue. The block copolymers are synthesized by sequential anionic and ring‐opening polymerization. The pH‐dependent micellization behaviour in aqueous solution of the triblock copolymers developed is studied using dynamic light scattering, zeta potential, transmission electron microscopy (TEM), and fluorimetric measurements. The shielding of the biotin at neutral pH and their availability at the micelle surface upon protonation is established by TEM and surface plasmon resonance with avidin and streptavidin‐coated gold surfaces. The preliminary stealthy behavior of these pH‐responsive micelles is examined using the complement activation (CH50) test.

Novel amphiphilic ABC miktoarm star terpolymers were synthesized that consist of hydrophilic poly(ethylene oxide) (PEO), hydrophobic poly( -caprolactone) (PCL), and pH-sensitive poly(2-vinylpyridine) (P2VP), thus a water-soluble block upon protonation. In the first step, poly(ethylene oxide monomethyl ether) (MPEO) was capped by one ω-epoxy end group by reaction of the original hydroxy end group with epichlorohydrin. MPEO-b-P2VP diblock copolymers were prepared by nucleophilic addition of living P2VP -Li + chains onto the epoxy group of MPEO's. Finally, the hydroxy group formed at the junction of the MPEO and P2VP blocks was used to initiate the ring-opening polymerization of -caprolactone in the presence of tin octoate. The ABC starshaped triblocks were characterized by 1 H NMR spectroscopy and size exclusion chromatography.

This work focused on the preparation and the aqueous solution properties of hybrid polymeric micelles consisting of a hydrophobic poly(epsilon-caprolactone) (PCL) core and a mixed shell of hydrophilic poly(ethylene oxide) (PEO) and pH-sensitive poly(2-vinylpyridine) (P2VP). The hybrid micelles were successfully prepared by the rapid addition of acidic water to a binary solution of PCL(34)-b-PEO(114) and PCL(32)-b-P2VP(52) diblock copolymers in N,N-dimethylformamide. These micelles were pH-responsive as result of the pH-dependent ionization of the P2VP block. The impact of pH on the self-assembly of the binary mixture of diblocks-thus on the composition, shape, size and surface properties of the micelles-was studied by a variety of experimental techniques, i.e., dynamic and static light scattering, transmission electron microscopy, Zeta potential, fluorescence spectroscopy and complement hemolytic 50 test.