Stimuli responsive star-shaped poly (N,N'-dimethylaminoethyl methacrylate-co-2-hydroxyethyl methacrylate)s P (DMAEMA-co-HEMA) bearing gluconamide-based unit with clickable functionality in the core were obtained by atom transfer radical polymerization (ATRP) and characterized in comparison with linear analogs. Next, hydroxyl groups in HEMA repeating units were used in the ring opening polymerization (ROP) of epsilon-caprolactone (CL) leading to comb and star-comb polymethacrylate-graft-polyester copolymers. The synthesized macromolecules showed the defined response to the temperature stimulus in water and PBS (pH 7.4) solutions depending on their composition, architecture as well as presence of additional PCL chains. The results of dynamic light scattering (DLS) measurements proved that composition of polymers strongly affected their self-assembling in the water solutions at room temperature and determined cloud point temperature (T-CP) in the range of 28.2-69.1 degrees C. Moreover, the techniques of atomic force microscopy and transmission electron microscopy (AFM, TEM) delivered visual manifestation of the variety of the structures created by polymers during the water evaporation, influenced by the changes in the morphology incident to the composition. The degree of auto-catalyzed hydrolysis of representative water-soluble linear and star-shaped copolymers reached the maximal amounts of 31% and 26%, pointing out that topology affects the extent of the process. (C) 2018 Elsevier Ltd. All rights reserved.