The influence of arm composition on the self-assembly of low-functionality telechelic star polymers in dilute solutions
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INVITED ARTICLE
The influence of arm composition on the self-assembly of low-functionality telechelic star polymers in dilute solutions Esmaeel Moghimi1,2 · Iurii Chubak3 · Dimitra Founta1,2 · Konstantinos Ntetsikas4 · George Polymeropoulos4 · Nikos Hadjichristidis4 · Christos N. Likos3 · Dimitris Vlassopoulos1,2 Received: 13 July 2020 / Revised: 15 August 2020 / Accepted: 23 August 2020 © The Author(s) 2020
Abstract We combine synthesis, physical experiments, and computer simulations to investigate self-assembly patterns of lowfunctionality telechelic star polymers (TSPs) in dilute solutions. In particular, in this work, we focus on the effect of the arm composition and length on the static and dynamic properties of TSPs, whose terminal blocks are subject to worsening solvent quality upon reducing the temperature. We find two populations, single stars and clusters, that emerge upon worsening the solvent quality of the outer block. For both types of populations, their spatial extent decreases with temperature, with the specific details (such as temperature at which the minimal size is reached) depending on the coupling between inter- and intra-molecular associations as well as their strength. The experimental results are in very good qualitative agreement with coarse-grained simulations, which offer insights into the mechanism of thermoresponsive behavior of this class of materials. Keywords Gels · Micelles · Nanoparticles · Polymer brushes · Polymer synthesis · Properties · Mechanical · Properties · Thermal · Self-assembly
Introduction Self-organization of building blocks due to external stimuli is ubiquitous in most materials and all living organisms in nature. Inspired by this, a remarkable body of work has been performed to understand and emulate their response to temperature [1–3], pH [4–6] and light [7, 8], enabling
E. M. and I. C. contributed equally. Christos N. Likos
[email protected] Dimitris Vlassopoulos
[email protected] 1
Institute of Electronic Structure and Laser, FORTH, 71110, Heraklion, Crete, Greece
2
Department of Materials Science, Technology, University of Crete, 71003, Heraklion, Crete, Greece
3
Faculty of Physics, University of Vienna, Boltzmanngasse 5, A-1090, Vienna, Austria
4
Physical Sciences and Engineering Division, KAUST Catalysis Center, Polymer Synthesis Laboratory, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955, Kingdom of Saudi Arabia
the controlled design of their structure assembly. Recent advances in polymer chemistry have led to the synthesis of various building blocks with complex architectures and functionalized properties. Such responsive building blocks that can self-organize into higher-order structures may form soft patchy particles, which have directional interactions and varying softness. Furthermore, topological effects that arise in systems with complex architecture can alone lead to a range of interesting phenomena in and out of thermodynamic equilibrium for both low [9– 15] and high system densities [16–21].
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