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Self-assembling of Thermo-Responsive Block Copolymers: Structural, Thermal and Dielectric Investigations

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Thermodynamics and Biophysics of Biomedical Nanosystems

Part of the book series: Series in BioEngineering ((SERBIOENG))

Abstract

Plethora of amphiphilic polymers and copolymers have been synthesized that form self-assembled structures in aqueous media, resembling the assemblies of biopolymers invented by nature. Such polymeric systems serve as stimuli-responsive materials, i.e. they respond to small external changes in the environmental conditions, which is a common process for biopolymers in living organisms. Temperature is the most widely used stimulus in environmentally responsive polymer systems. Thermoresponsive polymers have attracted much research interest because of their potential applications, which include rheological control additives, thermal affinity separation, controlled drug release, gene therapy and regenerative medicine. On the other hand, they represent model systems for many biological systems, for example for the investigation of the interaction between peptide-like groups and solvents and, thus, for the study of protein stability in aqueous solutions. In this chapter, we provide a comprehensive view on recent investigations on the micellar aggregation and the thermoresponsive behavior of amphiphilic model polymers. Firstly, we will present general characteristics of the thermoresponsive behavior of macromolecules and discuss in more detail their applications with biomedical interest. Next, we will focus on the experimental investigation of thermoresponsive polymers and present, briefly, research outcomes concerning the properties of the well-studied poly(N-isopropylacrylamide) (PNIPAM) polymer. Then, we will present results with respect to the thermoresponsive behavior of a rather new class of polymers based on the nonionic poly(methoxy diethylene glycol acrylate) (PMDEGA) polymer. Copolymers with various architectures, namely diblock, triblock and star block copolymers are studied, as well as a PMDEGA homopolymer as reference. To that aim, complementary methods were applied, such as small-angle X-ray (SAXS), differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS). Seeking for understanding of fundamental aspects of the macromolecular thermoresponsive behavior, we present, in a comparative way, results obtained on PNIPAM- and PMDEGA-based systems. Characteristic differences between the two series of polymeric solutions are worked out, concerning the self-organization, the width and hysteresis of the transition, and the chain conformations during the demixing phase transition.

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Acknowledgements

The authors would like to thank Dionysia Aravopoulou (NTUA), Achille M. Bivigou-Koumba, Anna Miasnikova (Universität Potsdam), Joseph Adelsberger, Konstantinos Kyriakos, Andreas Meier-Koll, Peter Müller-Buschbaum and Kordelia Troll (TU München) who were or are involved in studies of thermoresponsive polymers in our groups. Financial support was provided by Deutsche Forschungsgemeinschaft (DFG) via the priority program SPP 1259 “Intelligente Hydrogele” (grants LA611/7, MU1487/8 and PA771/4) and by the German Academic Exchange Service (DAAD) within the program “Hochschulpartnerschaften mit Griechenland” (ResComp).

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Authors and Affiliations

  1. Physics Department, National Technical University of Athens, Iroon Polytechneiou 9, Zografou Campus, 15780, Athens, Greece

    A. Kyritsis

  2. Fraunhofer Institut Für Angewandte Polymerforschung, Geiselbergstr. 69, 14476, Potsdam-Golm, Germany

    A. Laschewsky

  3. Physik-Department, Fachgebiet Physik Weicher Materie, Technische Universität München, James-Franck-Str. 1, 85748, Garching, Germany

    C. M. Papadakis

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  1. School of Pharmacy, National and Kapodistrian University of Athens, Athens, Greece

    Costas Demetzos

  2. School of Pharmacy, National and Kapodistrian University of Athens, Athens, Greece

    Natassa Pippa

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Kyritsis, A., Laschewsky, A., Papadakis, C.M. (2019). Self-assembling of Thermo-Responsive Block Copolymers: Structural, Thermal and Dielectric Investigations. In: Demetzos, C., Pippa, N. (eds) Thermodynamics and Biophysics of Biomedical Nanosystems. Series in BioEngineering. Springer, Singapore. https://doi.org/10.1007/978-981-13-0989-2_12

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