Thermodynamic Parameters of Temperature‐Induced Phase Transition for Brushes onto Nanoparticles: Hydrophilic versus Hydrophobic End‐Groups Functionalization

• Published in: Macromolecular rapid communications. 2017-10, Vol.38 (19), p.n/a
• Main Authors: Schweizerhof, Sjören, Demco, Dan Eugen, Mourran, Ahmed, Keul, Helmut, Fechete, Radu, Möller, Martin
• Format: Article
• Language: English
• Subjects: 1H NMR spectroscopy; Acrylic Resins - chemistry; Addition polymerization; Brushes; Chains (polymeric); Chemical synthesis; coil‐to‐globule transition; Entropy; Gold; Gold - chemistry; gold nanorods; Hydrophobic and Hydrophilic Interactions; Hydrophobicity; Isopropylacrylamide; Molecular Conformation; Molecular weight; Nanoparticles; Nanoparticles - chemistry; Nanorods; NMR; Nuclear magnetic resonance; Phase Transition; Phase transitions; poly(N‐isopropylacrylamide); polymer brush; Polymerization; Polymers; Polymers - chemistry; Spinning (materials); Stimuli; Surface Properties; Temperature effects; temperature‐induced phase transition; Thermodynamics; Transition Temperature
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.201700362

Quantification of the stimuli‐responsive phase transition in polymers is topical and important for the understanding and development of novel stimuli‐responsive materials. The temperature‐induced phase transition of poly(N‐isopropylacrylamide) (PNIPAm) with one thiol end group depends on the confinement—free polymer or polymer brush—on the molecular weight and on the nature of the second end. This paper describes the synthesis of heterotelechelic PNIPAm of different molecular weights with a thiol end group—that specifically binds to gold nanorods and a hydrophilic NIPAm end group by reversible addition‐fragmentation chain‐transfer polymerization. Proton high‐resolution magic angle sample spinning NMR spectra are used as an indicator of the polymer chain conformations. The characteristics of phase transition given by the transition temperature, entropy, and width of transition are obtained by a two‐state model. The dependence of thermodynamic parameters on molecular weight is compared for hydrophilic and hydrophobic end functional‐free polymers and brushes. Thermodynamic parameters of the temperature‐induced phase transition of heterotelechelic poly(N‐isopropylacrylamide) brushes grafted onto gold nanorods are studied by high‐resolution, magic‐angle sample spinning 1H NMR spectroscopy and compared to free polymer in aqueous solution. Transition temperature, entropy, and width of transition demonstrate remarkable differences depending on the molecular weight and polarity of the free terminal end groups.