Engineering a Multifunctional Nitroreductase for Improved Activation of Prodrugs and PET Probes for Cancer Gene Therapy

Cell Chem Biol. 2017 Mar 16;24(3):391-403. doi: 10.1016/j.chembiol.2017.02.005. Epub 2017 Mar 2.

Abstract

Gene-directed enzyme-prodrug therapy (GDEPT) is a promising anti-cancer strategy. However, inadequate prodrugs, inefficient prodrug activation, and a lack of non-invasive imaging capabilities have hindered clinical progression. To address these issues, we used a high-throughput Escherichia coli platform to evolve the multifunctional nitroreductase E. coli NfsA for improved activation of a promising next-generation prodrug, PR-104A, as well as clinically relevant nitro-masked positron emission tomography-imaging probes EF5 and HX4, thereby addressing a critical and unmet need for non-invasive bioimaging in nitroreductase GDEPT. The evolved variant performed better in E. coli than in human cells, suggesting optimal usefulness in bacterial rather than viral GDEPT vectors, and highlighting the influence of intracellular environs on enzyme function and the shaping of promiscuous enzyme activities within the "black box" of in vivo evolution. We provide evidence that the dominant contribution to improved PR-104A activity was enhanced affinity for the prodrug over-competing intracellular substrates.

Keywords: BDEPT; GDEPT; PET imaging; PR-104A; SOS response; directed evolution; metabolic interference; nitroimidazole; nitroreductase; substrate promiscuity.

MeSH terms

  • Binding Sites
  • Cell Line, Tumor
  • Escherichia coli / metabolism
  • Escherichia coli Proteins / chemistry
  • Escherichia coli Proteins / genetics
  • Escherichia coli Proteins / metabolism*
  • Etanidazole / analogs & derivatives
  • Etanidazole / chemistry
  • Etanidazole / metabolism
  • HCT116 Cells
  • Humans
  • Hydrocarbons, Fluorinated / chemistry
  • Hydrocarbons, Fluorinated / metabolism
  • Imidazoles / chemistry
  • Imidazoles / metabolism
  • Inhibitory Concentration 50
  • Metronidazole / chemistry
  • Metronidazole / metabolism
  • Molecular Docking Simulation
  • Mutagenesis, Site-Directed
  • Neoplasms / diagnosis
  • Neoplasms / pathology
  • Neoplasms / therapy*
  • Nitrogen Mustard Compounds / chemistry
  • Nitrogen Mustard Compounds / metabolism*
  • Nitroreductases / chemistry
  • Nitroreductases / genetics
  • Nitroreductases / metabolism*
  • Positron-Emission Tomography
  • Prodrugs / chemistry
  • Prodrugs / metabolism*
  • Protein Structure, Tertiary
  • Substrate Specificity
  • Triazoles / chemistry
  • Triazoles / metabolism

Substances

  • Escherichia coli Proteins
  • HX4 compound
  • Hydrocarbons, Fluorinated
  • Imidazoles
  • Nitrogen Mustard Compounds
  • PR-104A
  • Prodrugs
  • Triazoles
  • Metronidazole
  • Etanidazole
  • 2-(2-nitro-1H-imidazol-1-yl)-N-(2,2,3,3,3-pentafluoropropyl)acetamide
  • Nitroreductases