The structure-self-assembly relationship in PDMAEMA/polyester miktoarm stars

Well-defined miktoarm star-shaped polymers based on a heterofunctional glucose derivative initiator, N,N ′-dimethylaminoethyl methacrylate (DMAEMA) and various cyclic esters, such as -caprolactone (CL), lactide (LA), and glycolide (GA), were obtained by combining atom transfer radical polymerization...

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Bibliographic Details
Published in:Polymer chemistry 2022-08, Vol.13 (33), p.4763-4775
Main Authors: Miela czyk, Anna, Kupczak, Maria, Klymenko, Olesya, Miela czyk, ukasz, Arabasz, Sebastian, Madej, Krystian, Neugebauer, Dorota
Format: Article
Language:English
Subjects:
Block copolymers
Chemical reactions
Diameters
Diffraction patterns
Esters
Macromolecules
Phase transitions
Polyesters
Polymer chemistry
Polymerization
Ring opening polymerization
Self-assembly
Topology
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Summary:Well-defined miktoarm star-shaped polymers based on a heterofunctional glucose derivative initiator, N,N ′-dimethylaminoethyl methacrylate (DMAEMA) and various cyclic esters, such as -caprolactone (CL), lactide (LA), and glycolide (GA), were obtained by combining atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) techniques and then the click reaction. In addition, linear block copolymers PDMAEMA- b -polyester have been obtained to estimate how the topology alters the physicochemical properties of macromolecules. The measurements of the cloud point temperatures ( T CP ) and hydrodynamic diameters ( D h ) have shown that the presence of salts in polymer solutions affects the phase transformation, resulting in an increase in T CP values (48-55 °C in H 2 O; 60-80 °C in PBS, pH 7.4) and aggregate sizes ( D h : 9-290 nm in H 2 O; D h : 8-337 nm in PBS, pH 7.4, at 25 °C). The critical aggregation concentration (CAC) of miktoarm stars decreased with decreasing DMAEMA unit content. TEM and AFM measurements in the solid state revealed that some miktostars created fractals. The microstructure studies provided by TEM analysis in the dark field mode indicated semicrystalline phase formation above the CAC, with a regular diffraction pattern in the case of a miktoarm star with a poly(lactide- co -glycolide- co -caprolactone) arm. AFM analysis showed the changes of the 3D topography of samples with different compositions of polyester arms. Amphiphilic PDMAEMA/polyester miktoarm star-shaped polymers showed a structure-property correlation indicating their potential application as stimuli responsive solubilizing agents.
ISSN:1759-9954
1759-9962
DOI:10.1039/d2py00644h