Phosphorescent sensor for phosphorylated peptides based on an iridium complex

J Org Chem. 2014 Jul 3;79(13):6000-5. doi: 10.1021/jo5005263. Epub 2014 Jun 20.

Abstract

A bis[(4,6-difluorophenyl)pyridinato-N,C(2')]iridium(III) picolinate (FIrpic) derivative coupled with bis(Zn(2+)-dipicolylamine) (ZnDPA) was developed as a sensor (1) for phosphorylated peptides, which are related to many cellular mechanisms. As a control, a fluorescent sensor (2) based on anthracene coupled to ZnDPA was also prepared. When the total negative charge on the phosphorylated peptides was changed to -2, -4, and -6, the emission intensity of sensor 1 gradually increased by factors of up to 7, 11, and 16, respectively. In contrast, there was little change in the emission intensity of sensor 1 upon the addition of a neutral phosphorylated peptide, non-phosphorylated peptides, or various anions such as CO3(2-), NO3(-), SO4(2-), phosphate, azide, and pyrophosphate. Furthermore, sensor 1 could be used to visually discriminate between phosphorylated peptides and adenosine triphosphate in aqueous solution under a UV-vis lamp, unlike fluorescent sensor 2. This enhanced luminance of phosphorescent sensor 1 upon binding to a phosphorylated peptide is attributed to a reduction in the repulsion between the Zn(2+) ions due to the phenoxy anion, its strong metal-to-ligand charge transfer character, and a reduction in self-quenching.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adenosine Triphosphate / chemistry*
  • Coordination Complexes / chemistry*
  • Fluorescent Dyes / chemistry*
  • Ions / chemistry*
  • Iridium / chemistry*
  • Ligands
  • Molecular Structure
  • Peptides / chemistry*
  • Picolinic Acids / chemistry*

Substances

  • Coordination Complexes
  • Fluorescent Dyes
  • Ions
  • Ligands
  • Peptides
  • Picolinic Acids
  • bis((4,6-difluorophenyl)pyridinato-N,C(2'))iridium(III)picolinate
  • Iridium
  • Adenosine Triphosphate
  • picolinic acid