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Terpyridine-functionalized stimuli-responsive microgels and their assembly through metal-ligand interactions
Sungkyunkwan University, Republic of Korea .
Sungkyunkwan University, Republic of Korea .
Eötvös Loránd University, Hungary.
RISE - Research Institutes of Sweden, Bioscience and Materials, Surface, Process and Formulation. KTH Royal Institute of Technology, Sweden.
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2018 (English)In: Polymer Chemistry, ISSN 1759-9954, E-ISSN 1759-9962, Vol. 9, no 8, p. 1032-1039Article in journal (Refereed) Published
Abstract [en]

We developed a terpyridine-functionalized microgel (tpy-mG) for its supramolecular assembly. Tpy-mG was synthesized by amidation between 3-(4-([2,2′:6′,2′′-terpyridin]-4′-yl)phenoxy)propan-1-amine and carboxylates of a thermo-responsive p(NIPAM-co-MAA) microgel (A-mG), which was synthesized by emulsion polymerization. After decorating terpyridine, its effects on the hydrodynamic radius, volume phase transition temperature (VPTT), and the colloidal stability of the microgel were investigated. Tpy-mG can be assembled reversibly with several metal ions (Ni2+, Fe2+, Co2+, or Zn2+), and interestingly the assembled tpy-mG-M2+ showed different rheological properties depending on the metal ion type; the weakly bound ions (Co2+, Zn2+) indicated fast dynamics for "inter-particular" exchange, resulting in much higher storage (G′) and loss (G′′) moduli. Photocatalysts such as Ru dyes can be easily introduced into tpy-mGvia metal-ligand interactions, and the photooxidation of benzylamine was tested. The free Ru dye showed almost the same conversions at 25 and 50 °C, whereas the assembled Ru-tpy-mG-Mg2+ displayed reduced conversion at 50 °C (>VPTT). This is suggested to be due to the collapsed or "locked" structure around the photocatalytic center (Ru). Tpy-mG can be utilized as a good platform for developing responsive functional materials via reversible metal-ligand complexation.

Place, publisher, year, edition, pages
2018. Vol. 9, no 8, p. 1032-1039
Keyword [en]
Carboxylation, Emulsification, Emulsion polymerization, Functional materials, Gels, Ion exchange, Ligands, Metal ions, Metals, Phenoxy resins, Photooxidation, Zinc, Hydrodynamic Radius, Metal-ligand complexation, Metal-ligand interactions, Responsive functional materials, Rheological property, Stimuli-responsive microgels, Supramolecular assemblies, Volume phase transition, Ruthenium
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:ri:diva-33471DOI: 10.1039/c8py00016fScopus ID: 2-s2.0-85042417973OAI: oai:DiVA.org:ri-33471DiVA, id: diva2:1188797
Note

Funding details: NRF-2015R1D1A1A02062095, MOE, Ministry of Education; Funding details: DG DEVCO, Directorate-General for International Cooperation and Development; Funding details: NanoS3, REA, Research Executive Agency; Funding details: 290251, REA, Research Executive Agency; Funding details: Marie Curie Cancer Care; Funding details: NRF-2013K1A3A7A03078216, MSIP, Ministry of Science, ICT and Future Planning; Funding details: NRF, National Research Foundation of Korea; Funding details: FP7, Seventh Framework Programme; Funding text: This research was supported by the Basic Science Research Programs through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2015R1D1A1A02062095). This research was also supported partially by the International Cooperation Program through the NRF funded by the Ministry of Science, ICT & Future Planning (no. NRF-2013K1A3A7A03078216). This research has also received funding from the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme FP7/2007–2013/under REA grant agreement n.290251 (NanoS3).

Available from: 2018-03-08 Created: 2018-03-08 Last updated: 2018-03-16Bibliographically approved

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