Highly Stable and Luminescent Oxygen Nanosensor Based on Ruthenium-Containing Metallopolymer for Real-Time Imaging of Intracellular Oxygenation

ACS Sens. 2019 Apr 26;4(4):984-991. doi: 10.1021/acssensors.9b00131. Epub 2019 Mar 21.

Abstract

Metal complex-based luminescent oxygen nanosensors have been intensively studied for biomedical applications. In terms of monitoring dynamics of intracellular oxygen, however, high-quality nanosensors are still badly needed, because of stringent requirements on stability, biocompatibility and luminescence intensity, aside from oxygen sensitivity. In this paper, we reported a type of highly luminescent and stable oxygen nanosensors prepared from metallopolymer. First, a novel ruthenium(II)-containing metallopolymer was synthesized by chelating the oxygen probe [Ru(bpy)3]2+ with a bipyridine-branched hydrophobic copolymer, which was then doped into polymeric nanoparticles (NPs) by a reprecipitation method, followed by further conjugation to selectively target mitochondria (Mito-NPs). The resultant Mtio-NPs possessed a small hydrodynamic size of ∼85 nm, good biocompatibility and high stability resulting from PEGylation and stable nature of Ru-complex. Because the complexed [Ru(bpy)3]2+ homogeneously resided on particle surface, Mito-NPs exhibited strong luminescence at 608 nm that was free of aggregation-caused-quenching, the utmost oxygen sensitivity of free [Ru(bpy)3]2+ probe ( Q = 75%), and linear Stern-Volmer oxygen luminescence quenching plots. Taking advantage of the mitochondria-specific nanosensors, intracellular oxygenation and deoxygenation processes were real-time monitored for 10 min by confocal luminescence imaging, visualized by the gradual weakening (by more than 90%) and enhancing (by 50%) of the red emission, respectively.

Keywords: Ru complex; luminescence; metallopolymer; oxygen nanosensor; photostability.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acrylic Resins / chemical synthesis
  • Acrylic Resins / chemistry*
  • Acrylic Resins / toxicity
  • Coordination Complexes / chemical synthesis
  • Coordination Complexes / chemistry
  • Coordination Complexes / toxicity
  • Hep G2 Cells
  • Humans
  • Luminescence
  • Luminescent Agents / chemical synthesis
  • Luminescent Agents / chemistry*
  • Luminescent Agents / toxicity
  • Luminescent Measurements / methods
  • Microscopy, Confocal / methods
  • Mitochondria / metabolism*
  • Nanoparticles / chemistry*
  • Nanoparticles / toxicity
  • Oxygen / analysis*
  • Polystyrenes / chemical synthesis
  • Polystyrenes / chemistry*
  • Polystyrenes / toxicity
  • Proof of Concept Study
  • Ruthenium / chemistry
  • Ruthenium / toxicity

Substances

  • Acrylic Resins
  • Coordination Complexes
  • Luminescent Agents
  • Polystyrenes
  • tris(2,2-bipyridine)-ruthenium(II)
  • Ruthenium
  • Oxygen