Spontaneous CO release from Ru(II)(CO)2-protein complexes in aqueous solution, cells, and mice

Angew Chem Int Ed Engl. 2015 Jan 19;54(4):1172-5. doi: 10.1002/anie.201409344. Epub 2014 Dec 4.

Abstract

We demonstrate that Ru(II)(CO)2-protein complexes, formed by the reaction of the hydrolytic decomposition products of [fac-RuCl(κ(2)-H2NCH2CO2)(CO)3] (CORM-3) with histidine residues exposed on the surface of proteins, spontaneously release CO in aqueous solution, cells, and mice. CO release was detected by mass spectrometry (MS) and confocal microscopy using a CO-responsive turn-on fluorescent probe. These findings support our hypothesis that plasma proteins act as CO carriers after in vivo administration of CORM-3. CO released from a synthetic bovine serum albumin (BSA)-Ru(II)(CO)2 complex leads to downregulation of the cytokines interleukin (IL)-6, IL-10, and tumor necrosis factor (TNF)-α in cancer cells. Finally, administration of BSA-Ru(II)(CO)2 in mice bearing a colon carcinoma tumor results in enhanced CO accumulation at the tumor. Our data suggest the use of Ru(II)(CO)2-protein complexes as viable alternatives for the safe and spatially controlled delivery of therapeutic CO in vivo.

Keywords: CORM; albumin; carbon monoxide; metalloproteins; prodrugs.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Carbon Monoxide / analysis
  • Carbon Monoxide / metabolism
  • Cattle
  • Cell Line, Tumor
  • Female
  • HeLa Cells
  • Histidine / chemistry
  • Humans
  • Interleukin-10 / metabolism
  • Interleukin-6 / metabolism
  • Mass Spectrometry
  • Mice
  • Mice, Inbred BALB C
  • Neoplasms / drug therapy
  • Organometallic Compounds / chemistry*
  • Prodrugs / chemistry
  • Prodrugs / metabolism
  • Prodrugs / therapeutic use
  • Serum Albumin, Bovine / chemistry*
  • Serum Albumin, Bovine / metabolism
  • Tissue Distribution
  • Transplantation, Heterologous
  • Tumor Necrosis Factor-alpha / metabolism

Substances

  • Interleukin-6
  • Organometallic Compounds
  • Prodrugs
  • Tumor Necrosis Factor-alpha
  • tricarbonylchloro(glycinato)ruthenium(II)
  • Interleukin-10
  • Serum Albumin, Bovine
  • Histidine
  • Carbon Monoxide