Exponential Amplification Using Photoredox Autocatalysis

J Am Chem Soc. 2021 Aug 4;143(30):11544-11553. doi: 10.1021/jacs.1c04236. Epub 2021 Jul 21.

Abstract

Exponential molecular amplification such as the polymerase chain reaction is a powerful tool that allows ultrasensitive biodetection. Here, we report a new exponential amplification strategy based on photoredox autocatalysis, where eosin Y, a photocatalyst, amplifies itself by activating a nonfluorescent eosin Y derivative (EYH3-) under green light. The deactivated photocatalyst is stable and rapidly activated under low-intensity light, making the eosin Y amplification suitable for resource-limited settings. Through steady-state kinetic studies and reaction modeling, we found that EYH3- is either oxidized to eosin Y via one-electron oxidation by triplet eosin Y and subsequent 1e-/H+ transfer, or activated by singlet oxygen with the risk of degradation. By reducing the rate of the EYH3- degradation, we successfully improved EYH3--to-eosin Y recovery, achieving efficient autocatalytic eosin Y amplification. Additionally, to demonstrate its flexibility in output signals, we coupled the eosin Y amplification with photoinduced chromogenic polymerization, enabling sensitive visual detection of analytes. Finally, we applied the exponential amplification methods in developing bioassays for detection of biomarkers including SARS-CoV-2 nucleocapsid protein, an antigen used in the diagnosis of COVID-19.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • 3,3'-Diaminobenzidine / chemistry
  • Biomarkers / chemistry
  • Catalysis / radiation effects
  • Coronavirus Nucleocapsid Proteins / analysis*
  • Eosine Yellowish-(YS) / analogs & derivatives*
  • Eosine Yellowish-(YS) / chemical synthesis
  • Eosine Yellowish-(YS) / radiation effects
  • Fluorescence
  • Light
  • Limit of Detection
  • Oxidation-Reduction / radiation effects
  • Phosphoproteins / analysis
  • Polyethylene Glycols / chemistry
  • Polymerization
  • Proof of Concept Study
  • SARS-CoV-2 / chemistry
  • Spectrometry, Fluorescence / methods*

Substances

  • Biomarkers
  • Coronavirus Nucleocapsid Proteins
  • Phosphoproteins
  • nucleocapsid phosphoprotein, SARS-CoV-2
  • 3,3'-Diaminobenzidine
  • Polyethylene Glycols
  • monomethoxypolyethylene glycol
  • Eosine Yellowish-(YS)