Diblock Copolymer Formation via Self-Assembly of Cyclodextrin and Adamantyl End-Functionalized Polymers

Abstract

Two water-soluble polymers poly(2-methyl-2-oxazoline) and poly(N-isopropylacrylamide) with complexing moieties (β-CD and adamantane, respectively) located at the chain ends were prepared via controlled techniques. To verify the interaction of the β-CD- and adamantane-type polymer end groups in aqueous solution, detailed complexation studies were carried out by 1H NMR spectroscopy. It could be proved, that the polymers undergo self-assembly to form the corresponding supramolecular diblock structure. Furthermore, the double-hydrophilic block assembly was observed to be switchable to a hydrophilic−hydrophobic configuration by adjusting temperature leading to reversible aggregate formation.

Design Strategies for Functionalized Poly(2-oxazoline)s and Derived Materials

“…Diblock copolymers formed by the supramolecular assembly of β-cyclodextrinfunctionalized poly(N-isopropylacrylamide) and adamantine-end-capped pMeOx (for details, see reference [81]). …”

“…Supramolecular (thermoresponsive) diblock copolymers composed of two water-soluble polymers were obtained by Voit et al from β-cyclodextrin-functionalized poly(N-isopropylacrylamide) and adamantine-end-capped pMeOx (Scheme 7) [81]. The telechelic pMeOx was synthesized using adamantan-1-ylmethyl 4-(bromomethyl)-benzoate as initiator and 2-(iso-propylamino)ethanol as terminating agent.…”

Supramolecular glycopolymers with thermo-responsive self-assembly and lectin binding

“…[7][8][9] Similarly, stimuli-responsive or smart behavior can also be imparted to synthetic polymers by incorporation of functional groups that can undergo changes in physical properties, which allow the conjugation of other molecules, such as peptides, carbohydrates, targeting vectors or drugs, onto the polymer backbone. [25][26][27][28] Cyclodextrin and its derivatives are of great importance due to their well-known ability to incorporate hydrophobic molecules yielding inclusion complexes. 10,11 Smart polymers show rapid and reversible changes in response to small changes to their environment (e.g., pH, temperature, salt concentration, and co-solvent).…”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

“…Synthesis via organocatalyzed ringopening polymerization (Miao, et al, 2011) Cellulose with thymidineand/or trimethylammonium appendages at C6 Synthesis by carbohydrate-initiated cationic ring-opening polymerization Co-polymer with cyclodextrin and adamantly end-functionalized monomers TOF (HABA) Self-assembly by insertion of adamantine into cyclodextrin (Stadermann et al, 2011) Co-polymer of 3-hydroxybutyric acid and Dglucono--lactone…”