Browsing by Subject "AGGREGATION BEHAVIOR"

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  • Pooch, Fabian; Sliepen, Marjolein; Knudsen, Kenneth D.; Nyström, Bo; Tenhu, Heikki; Winnik, Francoise M. (2019)
    Poly(2-isopropyl-2-oxazoline)-b-poly(lactide) (PiPOx-b-PLA) diblock copolymers comprise two miscible blocks: the hydrophilic and thermosensitive PiPOx and the hydrophobic PLA, a biocompatible and biodegradable polyester. They self-assemble in water, forming stable dispersions of nanoparticles with hydrodynamic radii (R-h) ranging from similar to 18 to 60 nm, depending on their molar mass, the relative size of the two blocks, and the configuration of the lactide unit. Evidence from H-1 nuclear magnetic resonance spectroscopy, light scattering, small-angle neutron scattering, and cryo-transmission electron microscopy indicates that the nanoparticles do not adopt the typical core-shell morphology. Aqueous nanoparticle dispersions heated from 20 to 80 degrees C were monitored by turbidimetry and microcalorimetry. Nanoparticles of copolymers containing a poly(DL-lactide) block coagulated irreversibly upon heating to 50 degrees C, forming particles' of various shapes (R-h similar to 200-500 nm). Dispersions of PiPOx-b-poly(L-lactide) coagulated to a lesser extent or remained stable upon heating. From the entire experimental evidence, we conclude that PiPOx-b-PLA nanoparticles consist of a core of PLA/PiPOx chains associated via dipole-dipole interactions of the PLA and PiPOx carbonyl groups. The core is surrounded by tethered PiPOx loops and tails responsible for the colloidal stability of the nanoparticles in water. While the core of all nanoparticles studied contains associated PiPOx and PLA blocks, fine details of the nanoparticles morphology vary predictably with the size and composition of the copolymers, yielding particles of distinctive thermosensitivity in aqueous dispersions.
  • Kirila, Tatyana; Smirnova, Anna; Aseyev, Vladimir; Tenkovtsev, Andrey; Tenhu, Heikki; Filippov, Alexander (2021)
    The behavior of star-shaped six-arm poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines in aqueous solutions on heating was studied by light scattering, turbidimetry and microcalorimetry. The core of stars was hexaaza [2(6)] orthoparacyclophane and the arms were poly-2-ethyl-2-oxazine, poly-2-isopropyl-2-oxazine, poly-2-ethyl-2-oxazoline, and poly-2-isopropyl-2-oxazoline. The arm structure affects the properties of polymers already at low temperatures. Molecules and aggregates were present in solutions of poly-2-alkyl-2-oxazines, while aggregates of two types were observed in the case of poly-2-alkyl-2-oxazolines. On heating below the phase separation temperature, the characteristics of the investigated solutions did not depend practically on temperature. An increase in the dehydration degree of poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines led to the formation of intermolecular hydrogen bonds, and aggregation was the dominant process near the phase separation temperature. It was shown that the characteristics of the phase transition in solutions of the studied polymer stars are determined primarily by the arm structure, while the influence of the molar mass is not so significant. In comparison with literature data, the role of the hydrophobic core structure in the formation of the properties of star-shaped polymers was analyzed.