Thermoresponsive PDMAEMA Brushes: Effect of Gold Nanoparticle Deposition

J Phys Chem B. 2015 Aug 13;119(32):10348-58. doi: 10.1021/acs.jpcb.5b04757. Epub 2015 Jul 29.

Abstract

The paper addresses the effect of gold nanoparticle (Au-NP) deposition on the thermoresponsive volume phase transition of the weak polyelectrolyte poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. PDMAEMA brushes were synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP). The PDMAEMA/Au-NP composite brushes were fabricated by immersing the brush modified wafer in the Au-NP suspension. Atomic force microscopy (AFM), ellipsometry, and scanning electron microscopy (SEM) have been employed to characterize the neat PDMAEMA brushes and PDMAEMA/Au-NP composite brushes. All neat PDMAEMA brushes swelled below the volume phase transition temperature and collapsed with increasing temperature over a broad temperature range independent of the initial brush thickness. Water uptake of the brushes is also independent of initial brush thickness. The adsorption of the charged Au-NPs significantly affects the degree of swelling and the thermoresponsive properties of the brushes. PDMAEMA/Au-NP composite brushes do not exhibit any noticeable phase transition at the experimental temperature range irrespective of the initial brush thickness. The reason for this behavior is attributed to a combination of the following: the decreased conformational entropy of the Au-NP adsorbed polymer chains, the increased hydrophilicity of the system due to the charged Au-NPs, and the ≈13 nm diameter Au-NPs causing steric hindrance. We have also shown that the AFM full-indentation method can be successfully applied to determine the polymer brush thicknesses.

MeSH terms

  • Gold / chemistry*
  • Metal Nanoparticles / chemistry*
  • Methacrylates / chemistry*
  • Microscopy, Atomic Force
  • Microscopy, Electron, Scanning
  • Nylons / chemistry*
  • Phase Transition
  • Surface Properties
  • Temperature*
  • Water / chemistry

Substances

  • Methacrylates
  • Nylons
  • poly(2-(dimethylamino)ethyl methacrylate)
  • Water
  • Gold