Ultra-Small Pd(0) Nanoparticles into a Designed Semisynthetic Lipase: An Efficient and Recyclable Heterogeneous Biohybrid Catalyst for the Heck Reaction under Mild Conditions

Molecules. 2018 Sep 14;23(9):2358. doi: 10.3390/molecules23092358.

Abstract

A novel heterogeneous enzyme-palladium (Pd) (0) nanoparticles (PdNPs) bionanohybrid has been synthesized by an efficient, green, and straightforward methodology. A designed Geobacillus thermocatenulatus lipase (GTL) variant genetically and then chemically modified by the introduction of a tailor-made cysteine-containing complementary peptide- was used as the stabilizing and reducing agent for the in situ formation of ultra-small PdNPs nanoparticles embedded on the protein structure. This bionanohybrid was an excellent catalyst in the synthesis of trans-ethyl cinnamate by Heck reaction at 65 °C. It showed the best catalytic performance in dimethylformamide (DMF) containing 10⁻25% of water as a solvent but was also able to catalyze the reaction in pure DMF or with a higher amount of water as co-solvent. The recyclability and stability were excellent, maintaining more than 90% of catalytic activity after five cycles of use.

Keywords: Heck reaction; heterogeneous catalyst; lipase; palladium nanoparticles; semisynthetic enzyme.

MeSH terms

  • Bacterial Proteins / chemical synthesis
  • Bacterial Proteins / chemistry
  • Bacterial Proteins / genetics
  • Catalysis
  • Dimethylformamide / chemistry*
  • Enzyme Stability
  • Geobacillus / enzymology*
  • Geobacillus / genetics
  • Lipase / chemical synthesis*
  • Lipase / chemistry
  • Lipase / genetics
  • Metal Nanoparticles / chemistry
  • Models, Molecular
  • Mutation
  • Palladium / chemistry*
  • Protein Conformation

Substances

  • Bacterial Proteins
  • Palladium
  • Dimethylformamide
  • Lipase