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Coupling interactions are strongest between NMR-active nuclei bonded to each other, where spin information can be transmitted directly through the pair of bonding electrons. While nuclei polarize their electrons to the opposite spins, the bonding electron pair has opposite spins. Configurations with antiparallel nuclear spins are expected to be lower in energy. When coupling makes antiparallel states more favorable, J is considered to have a positive value. The one-bond coupling constant, 1J,...
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In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
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IridiumIII Luminescent Probe for Detection of the Malarial Protein Biomarker Histidine Rich Protein-II
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Mitochondria-targeted spin-labelled luminescent iridium anticancer complexes.

V Venkatesh1,2, Raul Berrocal-Martin3, Christopher J Wedge4

  • 1Department of Chemistry , University of Warwick , Coventry CV4 7AL , UK .

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New iridium(iii) complexes targeting mitochondria show potent anticancer activity. The complex with two TEMPO labels (Ir-TEMPO2) demonstrated superior antiproliferative and antioxidant effects, especially against prostate cancer cells.

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Area of Science:

  • Inorganic Chemistry
  • Medicinal Chemistry
  • Cancer Biology

Background:

  • Mitochondrial dysfunction is a hallmark of cancer.
  • Targeting mitochondrial metabolism offers a promising therapeutic strategy.
  • Cyclometallated iridium(iii) complexes are explored for their potential in cancer treatment.

Purpose of the Study:

  • To design and synthesize novel cyclometallated iridium(iii) complexes with TEMPO spin labels.
  • To investigate the photophysical properties and mitochondrial localization of these complexes.
  • To evaluate their antiproliferative and antioxidant activities against various cancer cell lines.

Main Methods:

  • Synthesis of iridium(iii) complexes with one (Ir-TEMPO1) and two (Ir-TEMPO2) TEMPO spin labels.
  • Electron paramagnetic resonance (EPR) spectroscopy to study spin-spin interactions.
  • Luminescence spectroscopy to determine lifetimes and decay kinetics.
  • Density functional theory (DFT) calculations for conformational analysis.
  • In vitro antiproliferative assays (IC50 determination) and antioxidant activity assays.
  • Confocal microscopy for cellular localization studies.

Main Results:

  • Ir-TEMPO2 exhibited spin-spin interactions between TEMPO units, unlike Ir-TEMPO1.
  • Both complexes displayed luminescence with long lifetimes; Ir-TEMPO2 showed biexponential decay, indicating conformational flexibility.
  • Ir-TEMPO2 demonstrated significantly higher antiproliferative activity than Ir-TEMPO1 across cancer cell lines.
  • Ir-TEMPO2 possessed superior antioxidant activity against ovarian cancer cells.
  • Ir-TEMPO2 was highly potent against PC3 prostate cancer cells (IC50 = 0.53 microM), outperforming cisplatin and showing enhanced selectivity.
  • Both complexes were localized in the mitochondria of cancer cells.

Conclusions:

  • The presence of two TEMPO labels in Ir-TEMPO2 enhances its anticancer efficacy and antioxidant properties.
  • Ir-TEMPO2 represents a highly potent and selective mitochondria-targeting agent for prostate cancer therapy.
  • These iridium(iii)-TEMPO complexes hold significant promise for developing novel cancer therapeutics.