Synthesis and evaluation of bifunctional tetrahydroxamate chelators for labeling antibodies with 89Zr for imaging with positron emission tomography

Bioorg Med Chem Lett. 2018 Mar 1;28(5):899-905. doi: 10.1016/j.bmcl.2018.01.067. Epub 2018 Feb 2.

Abstract

Two novel bifunctional tetrahydroxamate chelators 3 and 4 were synthesized and evaluated for labeling antibodies with 89Zr for positron emission tomography imaging. Compared to previously reported tetrahydroxamate chelators 1 and 2 with an iminodiacetamide backbone, 3 and 4 were based on an extended iminodipropionamide and dipropylenetriamine backbone, respectively. Trastuzumab conjugates of 3 and 4 were efficiently labeled with 89Zr (>95% radiochemical yield). The in vitro plasma stability of 89Zr-4-Trastuzumab and especially 89Zr-3-Trastuzumab was greatly improved over previously reported 89Zr-1-Trastuzumab and 89Zr-2-Trastuzumab, but their demetalation remained higher and faster than 89Zr-deferoxamine (DFO)-Trastuzumab. These observations were confirmed by PET imaging and biodistribution in mice, with significant higher bone uptake for 89Zr-4-Trastuzumab, followed by 89Zr-3-Trastuzumab, and to a lesser extent for 89Zr-DFO-Trastuzumab. Molecular modeling showed that 3 and 4 with an extended backbone could form eight-coordinate Zr-complexes as compared to only seven-coordinate Zr-complexes of 1 and 2. Our data suggest further elongation of linker length between hydroxamate motifs of this class of chelators is needed to reach a better Zr-coordination configuration and improve in vivo stability.

Keywords: Molecular imaging; Monoclonal antibody; Positron emission tomography; Tetrahydroxamate chelator; Zirconium-89.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Animals
  • Antibodies, Monoclonal / chemistry*
  • Chelating Agents / chemical synthesis
  • Chelating Agents / chemistry*
  • Dose-Response Relationship, Drug
  • Female
  • Humans
  • Hydroxamic Acids / chemical synthesis
  • Hydroxamic Acids / chemistry*
  • Isotope Labeling
  • Mice
  • Models, Molecular
  • Molecular Structure
  • Neoplasms, Experimental / diagnostic imaging*
  • Positron-Emission Tomography*
  • Structure-Activity Relationship
  • Zirconium / chemistry*

Substances

  • Antibodies, Monoclonal
  • Chelating Agents
  • Hydroxamic Acids
  • Zirconium

Grants and funding