Reversible Surface Engineering via Nitrone-Mediated Radical Coupling

  • chair:

    Laun, J. / Marchal, W. / Trouillet, V. / Welle, A. / Hardy, A. / Van Bael, M.K. /  Barner-Kowollik, C. / Junkers, T. (2018)

  • place:

    Langmuir, 2018, 13, 34, 10, 3244-3255, doi: 10.1021/acs.langmuir.7b03167

  • Date: Februar 2018


Efficient and simple polymer conjugation reactions are critical for introducing functionalities on surfaces. For polymer surface grafting, postpolymerization modifications are often required, which can impose a significant synthetic hurdle. Here, we report two strategies that allow for reversible surface engineering via nitrone-mediated radical coupling (NMRC). Macroradicals stemming from the activation of polymers generated by copper-mediated radical polymerization are grafted via radical trapping with a surface-immobilized nitrone or a solution-borne nitrone. Since the product of NMRC coupling features an alkoxyamine linker, the grafting reactions can be reversed or chain insertions can be performed via nitroxide-mediated polymerization (NMP). Poly( n-butyl acrylate) ( Mn = 1570 g·mol-1, D̵ = 1.12) with a bromine terminus was reversibly grafted to planar silicon substrates or silica nanoparticles as successfully evidenced via X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry, and grazing angle attenuated total reflection Fourier-transform infrared spectroscopy (GAATR-FTIR). NMP chain insertions of styrene are evidenced via GAATR-FTIR. On silica nanoparticles, an NMRC grafting density of close to 0.21 chains per nm2 was determined by dynamic light scattering and thermogravimetric analysis. Concomitantly, a simple way to decorate particles with nitroxide radicals with precise control over the radical concentration is introduced. Silica microparticles and zinc oxide, barium titanate, and silicon nanoparticles were successfully functionalized.