Citation: Kang Ma, Yu-lu Ma, Hai-li Zhao, Song Liu, Lin-sheng Xie, Jin Sha. Fabrication of Hyperbranched PEG Brushes viaLaser-mediated Self-condensing Surface-initiated Atom Transfer Radical Polymerization[J]. Acta Polymerica Sinica, ;2018, 0(5): 571-580. doi: 10.11777/j.issn1000-3304.2017.17178 shu

Fabrication of Hyperbranched PEG Brushes viaLaser-mediated Self-condensing Surface-initiated Atom Transfer Radical Polymerization

Engineering Center of Efficient Green Process Equipment and Energy Conservation of Ministry of Education, School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai 200237

Corresponding author: Jin Sha, sjin@ecust.edu.cn
Received Date: 7 July 2017
Revised Date: 30 July 2017
Available Online: 1 March 2018

Surface polymer brushes have been extensively studied to modify the surface properties of substrates and to implement multifunctionality. Compared to comb type brushes, hyperbranched-structure polymer brushes show significant advantages in thermal stability, compatibility and functionalization potential. The preparation study of surface hyperbranched polymer brushes is fundamental to explode polymer brushes applications. Here, laser-mediated surface-initiated atom transfer radical polymerization (SI-ATRP) is firstly introduced to conduct self-condensing polymerization, with 2-bromoisobutyrate ester of oligo (ethylene glycol) methacrylate (OEGMA-Br) as AB^*-type inimer and Ir(ppy)₃ as the photo-redox catalyst, to prepare hyperbranched poly(ethylene glycol)(PEG) brushes on a silicon substrate. Based on the discussion on the mechanism of OEGMA-Br inimer self-condensing polymerization on solid-liquid interface and at surface solution on silicon surface, five microstructures are proposed for the constitution of the hyperbranched PEG brushes and the corresponding signals are further confirmed by ¹H-NMR spectra analysis. X-ray photoelectron spectroscopy (XPS) characterization is conducted to investigate the chemical composition of hyperbranched PEG brushes. The high resolution C1s and Br3d spectra indicate the preservation of surface bromine density on hyperbranched PEG brushes in comparison to initiator surface on silicon substrate, implying the hyperbranched microstructure and high active site densities. Then, the thickness of hyperbranched PEG brushes corresponding to different inimer concentrations is investigated by ellipsometry, which indicates an increase first in the thickness and a subsequant decrease trend as the inimer concentration increased. A competitive mechanism for the surface polymerization is proposed to depict the growth of the hyperbranched PEG brushes on a silicon substrate, which refers to a competition between the solid-liquid interface polymerization and the surface solution polymerization. An increase of inimer concentration would promote the self-condensing polymerization of the inimer in solution, which consequently inhibits the solid-liquid interface polymerization and is unfavorable to the hyperbranched PEG brushes growth. Furthermore, laser confocal microscopy observation of the absorption of 5-isothiocyanatofluorescein (FITC) labeled bovine serum albumin (BSA) on hyperbranched PEG brushes micropatterns proves the significant anti-fouling property. The research extends the application of photo-catalyzed SI-ATRP in the preparation of surface hyperbranched-structure polymer brushes, and provides fundamental technical support to expand the applications of the hyperbranched PEG brushes in drug transport, biosensing and high-throughput cell screening.
- Surface-initiated atom transfer radical polymerization,
- Hyperbranched structure,
- Poly(ethylene glycol) brush,
- Micropattern
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