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Delft University of Technology Block Copolymer Nanofibrillar Micelles Delft University of Technology Block Copolymer Nanofibrillar Micelles gelation, manipulation and applications Zhang, Kai DOI 10.4233/uuid:b5fd172c-b0ac-4023-851e-88b7d0ca31c5 Publication date 2018 Document Version Final published version Citation (APA) Zhang, K. (2018). Block Copolymer Nanofibrillar Micelles: gelation, manipulation and applications. https://doi.org/10.4233/uuid:b5fd172c-b0ac-4023-851e-88b7d0ca31c5 Important note To cite this publication, please use the final published version (if applicable). Please check the document version above. Copyright Other than for strictly personal use, it is not permitted to download, forward or distribute the text or part of it, without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license such as Creative Commons. Takedown policy Please contact us and provide details if you believe this document breaches copyrights. We will remove access to the work immediately and investigate your claim. This work is downloaded from Delft University of Technology. For technical reasons the number of authors shown on this cover page is limited to a maximum of 10. Block Copolymer Nanofibrillar Micelles: gelation, manipulation and applications Kai ZHANG Block Copolymer Nanofibrillar Micelles: gelation, manipulation and applications Proefschrift ter verkrijging van de grad van doctor aan de Technische Universiteit Delft, op gezag van de Rector Magnificus prof. dr. ir. T. H. J. J. van der Hagen, voorzitter van het College voor Promoties, in het openbaar te verdedigen op maandag 9 april 2018 om 12:30 uur door Kai ZHANG Master of Science in Polymer Science and Engineering, Sichuan University, China geboren te Hubei, China Dit proefschrift is goedgekeurd door de: promotor: Prof. dr. J. H. van Esch copromotor: Dr. hab. E. Mendes Samenstelling promotiecommissie: Rector Magnificus Technische Universiteit Delft voorzitter Prof. dr. J. H. van Esch Technische Universiteit Delft promotor Dr. hab. E. Mendes Technische Universiteit Delft copromotor Onafhankelijke leden: Prof. dr. P. Dubruel Universiteit Gent Prof. dr. A. Kros Universiteit Leiden Prof. dr. R. P. Sijbesma Technische Universiteit Eindhoven Prof. dr. S. J. Picken Technische Universiteit Delft Dr. C. Marques Instituut Charles Sadron, CNRS, France Prof. dr. E. J. R. Sudhӧlter Technische Universiteit Delft reservelid The work described in this thesis was carried out in the Advanced Soft Matter group at Delft University of Technology. This research was financially supported by China Scholarship Council. Cover design by Kai Zhang Copyright © 2018 by Kai Zhang ISBN: 978-94-6186-917-3 Printed by :Gildeprint - Enschede All rights reserved. The author encourages the communication of scientific contents and explicitly allows reproduction for scientific purposes provided the proper citation of the source. Parts of this thesis have been published in scientific journals and copyright is subject to different terms and conditions. To my family Contents 1. Introduction .................................................................................................................................. 1 1.1. Self-assembly of block copolymers .................................................................................................... 2 1.2. Manipulation of block copolymer micelles ........................................................................................ 5 1.3. Nano-fibril micellar hydrogels ............................................................................................................ 7 1.4. Challenges .......................................................................................................................................... 8 1.5. Outline of this thesis ........................................................................................................................... 8 1.6. References .......................................................................................................................................... 9 2. Hydrogels from block copolymer nanofibrillar micelles: thermal fusion crosslinking of micellar cores and/or chemical crosslinking of coronas ................................................................... 15 2.1. Introduction ...................................................................................................................................... 17 2.2. Results and Discussion ..................................................................................................................... 18 2.2.1. Formation of wormlike micelles ................................................................................................ 18 2.2.2. Physically crosslinked micellar hydrogels .................................................................................. 21 2.2.3. Chemically crosslinked micellar hydrogels ................................................................................ 25 2.3. Conclusion ........................................................................................................................................ 30 2.4. Experimental section ........................................................................................................................ 30 2.4.1. Materials .................................................................................................................................... 30 2.4.2. Modification of PS-b-PEO .......................................................................................................... 30 2.4.3. Preparation of nano-fibrous micelles and micellar gels ............................................................ 31 2.4.4. Characterization ........................................................................................................................ 31 2.5. References ........................................................................................................................................ 32 2.6. Appendix ........................................................................................................................................... 35 3. A facile approach for the fabrication of 2D supermicelle networks ............................................. 41 3.1. Introduction ...................................................................................................................................... 43 3.2. Results and Discussion ..................................................................................................................... 43 3.3. Conclusion ........................................................................................................................................ 49 3.4. Experimental section ........................................................................................................................ 49 3.4.1. Preparation of Ultralong micelles ............................................................................................. 49 3.4.2. Fabrication of PDMS stamp ....................................................................................................... 49 I 3.4.3. Alignment of ultralong micelles ................................................................................................ 50 3.4.4. Transfer printing of aligned micelles onto receiver substrate .................................................. 50 3.4.5. Characterization ........................................................................................................................ 51 3.5. References ........................................................................................................................................ 51 3.6. Appendix ........................................................................................................................................... 53 4. Patterned nano-fibrous micelles of block copolymers for controlled cell alignment..................... 61 4.1. Introduction ...................................................................................................................................... 63 4.2. Results and Discussion ..................................................................................................................... 64 4.2.1. Fabrication of micellar platform ................................................................................................ 64 4.2.2. Unidirectional micelles .............................................................................................................. 67 4.2.3. Multidirectional micelles ........................................................................................................... 71 4.3. Conclusions ....................................................................................................................................... 73 4.4. Experimental section ........................................................................................................................ 74 4.4.1. Synthesis and preparation of micelles ...................................................................................... 74 4.4.2. Fabrication of PDMS stamp ....................................................................................................... 75 4.4.3. Alignment of micelles ................................................................................................................ 75 4.4.4. Printing and crosslinking micelles onto glass slides .................................................................
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