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Table of contents
Chapter 1: Literature review: Hierarchical self-assembly via cyclodextrin-mediated host-guest interactions
Table of contents
Introduction
1. Driving forces, building blocks and variety of architectures of hierarchically self-assembled systems
1.1 Inorganic and hybrid hierarchically self-assembled materials
1.2 Soft matter hierarchically self-assembled materials
2. Hierarchical self-assembly mediated by Host-guest interactions
2.1 Nanoscale hierarchical systems based on cyclodextrins
2.1.1 Gene delivery systems
2.1.2 Various drug delivery-oriented nanoscale systems
2.2 Host-guest mediated supramolecular hydrogels
2.2.1 Hierarchical hydrogels formed from cyclodextrin-based polypseudorotaxanes
2.2.2 Cyclodextrin-based hierarchical hydrogels with external stimuli responsive properties
Conclusions
References
Chapter 2: Host-guest polymers with hydrophilic poly(ethylene glycol) spacer, their inclusion properties and self-assembly in water
Table of contents
Introduction
1. Synthesis of the host-guest polymers with hydrophilic PEG spacer
1.1 General synthetic strategy
1.2 Synthesis of thiolated dextrans (DT40-SH)
1.3 Synthesis of host polymers with hydrophilic PEG spacer (DT40-g-PEG-βCD)
1.3.1 Steglich esterification of poly(ethylene glycol) acrylate with 5-hexynoic acid
1.3.2 Nucleophile-mediated thiol-Michael click of DT40-SH and PEG-acryloyl-5-hexynoate
1.3.3 Synthesis of 6-Monodeoxy-6-monoazido-βCD (βCD-N3)
1.3.4 Synthesis of DT40-g-PEG-βCD by copper(I)-catalyzed azide-alkyne cycloaddition
1.4 Synthesis of guest polymers with hydrophilic PEG spacer (DT40-g-PEG-Ada)
1.4.1 Synthesis of hetero-bifunctionalized PEG-acrylate-Ada
1.4.2 Synthesis of DT40-g-PEG-Ada guest polymers
2. Binding properties of host-guest polymers with hydrophilic PEG spacers
2.1 Guest polymers – DT40-gPEG-Ada
2.1.1 Isothermal titration microcalorimetry studies
2.1.2 Surface plasmon resonance studies
2.2 Host polymers – DT40-gPEG-βCD
2.2.1 Isothermal titration microcalorimetry studies
2.2.2 Surface plasmon resonance studies
3. Nanoassemblies prepared from host-guest polymers with hydrophilic PEG spacers
3.1 Size and stability of HG-nanoassemblies by DLS
3.1.1 Effect of the stock solutions aging
3.1.2 Nanoassemblies stability by DLS
3.1.3 Minimal required DT40-gPEG-Ada2 aging time
3.1.4 Control experiment with βCD aiming to disrupt hydrophobic Ada-conglomerates in fresh DT40-gPEG-Ada2 solutions
3.2 SAXS and SLS investigation of the individual polymers and HG-nanoassemblies of different types
3.2.1 Individual host- and guest polymers
3.2.2 Host-guest nanoparticles of different types
Conclusions
Experimental section
Materials and reagents
Methods and instrumentation
Synthetic procedures
References
Chapter 3: Bifunctionalized dextrans for surface PEGylation via multivalent host-guest interactions
Table of contents
Introduction
a. PEG and PEGylation. General information
b. βCD host-guest chemistry and PEGylation
1. Synthesis of PEGylated guest polymers – D40-XGP-YAda-ZPEG
2. Binding properties of D40-GP-Ada-PEG in solution. ITC studies
3. Binding properties of D40-GP-Ada-PEG on the surface. SPR studies
3.1. Adsorption kinetics by SPR
Conclusions
Experimental section
Materials and reagents
Methods and instrumentation
Synthetic procedures
References
Chapter 4: Poly(N-isopropylacrylamide)-based hierarchical microgels: sterical stabilization of the particles and supramolecular hydrogel formation via host-guest int
Table of contents
Introduction
a. Sterically stabilized pNIPAm-g-pAAc/pβCDN+ hierarchical microgels
b. Supramolecular hydrogels based on pNIPAm/βCD1.62N hierarchical microgels
1. Sterically stabilized hierarchical pNIPAm-based microgels via host-guest interactions – pNIPAm βCDN/PEG
1.1 Preparation of host polymer coated pNIPAm microgels – pNIPAm/βCDN
1.1.1 pNIPAm-g-pAAc microgels
1.1.2 Host polymer coated pNIPAm/βCDN microgels
1.1.3 Evidence of βCDN+ coating
1.1.4 TC analysis of unbound βCDN+
1.1.5 Influence of βCDN+ charge density
1.2. Steric stabilization of the particles with DT40-GP-Ada-PEG
1.2.1 Strategy of steric stabilization
1.2.2 Estimation of surface PEG chains conformation
1.3 Thermoresponsive properties of pNIPAm/βCD1.62N and pNIPAm/βCD1.62N/PEG hierarchical microgels
2. Hierarchical hydrogels based on pNIPAm/βCDN through host-guest interactions
2.1 Hydrogels based on host-guest interactions between pβCD1.62N+ and DT110Ada
2.1.1 Rheological properties
2.2 Hydrogels based on host-guest interactions between pβCD3.24N+ and DT500Ada
2.2.1 Rheological properties
2.2.1. Freeze-drying pathway for the preparation of pNIPAm/βCD3.24N/DT500Ada2 hydrogels
Conclusions
Experimental section
Materials and reagents
Methods and instrumentation
References
General conclusions and perspectives



