Enhanced Peroxidase-Like Performance of Gold Nanoparticles by Hot Electrons

Chemistry. 2017 May 17;23(28):6717-6723. doi: 10.1002/chem.201605380. Epub 2017 Mar 29.

Abstract

Enzyme mimics have been widely used as alternatives to natural enzymes. However, the catalytic performances of enzyme mimics are often decreased due to different spatial structures or absence of functional groups compared to natural enzymes. Here, we report a highly efficient enzyme-like catalytic performance of gold nanoparticles (AuNPs) by visible-light stimulation. The enzyme-like reaction is evaluated by the catalytic reaction of AuNPs oxidizing a typical chromogenic substrate 3,3',5,5'-tetramethylbenzydine (TMB) with hydrogen peroxide as an oxidant. From investigations of the wavelength-dependent reaction rate, radical capture, hole-donor addition, and dark-field scattering spectroscopy experiments, it is revealed that the strong plasmonic absorption of AuNPs facilitates generation of hot electrons, which are transfered from AuNPs to the adsorbed reactant molecule, greatly promoting the catalytic performance of the enzyme-like catalytic reaction. The present work provides a simple method for improving the performance of enzyme mimics, which is expected to find further application in the field of plasmon-enhanced biocatalysis and biosensors.

Keywords: enzyme mimics; gold nanoparticles; hot electrons; localized surface plasmon resonance; reaction mechanism.

MeSH terms

  • Biocompatible Materials / chemistry*
  • Biocompatible Materials / metabolism
  • Biosensing Techniques
  • Catalysis
  • Electrons
  • Gold / chemistry*
  • Hydrogen Peroxide / chemistry
  • Kinetics
  • Light
  • Metal Nanoparticles / chemistry*
  • Peroxidase / chemistry
  • Peroxidase / metabolism
  • Spectrophotometry
  • Surface Plasmon Resonance

Substances

  • Biocompatible Materials
  • Gold
  • Hydrogen Peroxide
  • Peroxidase