Enantiopure bifunctional chelators for copper radiopharmaceuticals--does chirality matter in radiotracer design?

Eur J Med Chem. 2014 Jun 10:80:308-15. doi: 10.1016/j.ejmech.2014.04.071. Epub 2014 Apr 25.

Abstract

It is well recognized that carbon chirality plays a critical role in the design of drug molecules. However, very little information is available regarding the effect of stereoisomerism of macrocyclic bifunctional chelators (BFC) on biological behaviors of the corresponding radiopharmaceuticals. To evaluate such effects, three enantiopure stereoisomers of a copper radiopharmaceutical BFC bearing two chiral carbon atoms were synthesized in forms of R,R-, S,S-, and R,S-. Their corresponding peptide conjugates were prepared by coupling with a model peptide sequence, c(RGDyK), which targets the αvβ3 integrin for in vitro and in vivo evaluation of their biological behaviors as compared to the racemic conjugate. Despite the chirality differences, all the conjugates showed a similar in vitro binding affinity profile to the αvβ3 integrin (106, 108, 85 and 100 nM for rac-H2-1, RR-H2-1, SS-H2-1, and RS-H2-1 respectively with all p values > 0.05) and a similar level of in vivo tumor uptake (2.72 ± 0.45, 2.60 ± 0.52, 2.45 ± 0.48 and 2.88 ± 0.59 for rac-(64)Cu-1, RR-(64)Cu-1, SS-(64)Cu-1, and RS-(64)Cu-1 at 1 h p.i. respectively). Furthermore, they demonstrated a nearly identical biodistribution pattern in major organs (e.g. 2.07 ± 0.21, 2.13 ± 0.58, 1.70 ± 0.20 and 1.90 ± 0.46 %ID/g at 24 h p.i. in liver for rac-(64)Cu-1, RR-(64)Cu-1, SS-(64)Cu-1, and RS-(64)Cu-1 respectively; 1.80 ± 0.46, 2.30 ± 1.49, 1.73 ± 0.31 and 2.23 ± 0.71 at 24 h p.i. in kidneys for rac-(64)Cu-1, RR-(64)Cu-1, SS-(64)Cu-1, and RS-(64)Cu-1 respectively). Therefore we conclude that the chirality of BFC plays a negligible role in αvβ3-targeted copper radiopharmaceuticals. However, we believe it is still worthwhile to consider the chirality effects of BFCs on other targeted imaging or therapeutic agents.

Keywords: Bifunctional chelator (BFC); Copper-64; Diagnosis; Imaging; Integrin α(v)β(3); Molecular imaging; Positron emission tomography; Prognosis.

Publication types

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

MeSH terms

  • Animals
  • Cell Line, Tumor
  • Chelating Agents / chemistry*
  • Copper Radioisotopes*
  • Drug Design
  • Humans
  • Integrin alphaVbeta3 / metabolism
  • Macrocyclic Compounds / chemistry*
  • Male
  • Mice
  • Positron-Emission Tomography
  • Radioactive Tracers
  • Radiochemistry
  • Radiopharmaceuticals / chemistry*
  • Radiopharmaceuticals / metabolism
  • Radiopharmaceuticals / pharmacokinetics
  • Stereoisomerism
  • Structure-Activity Relationship
  • Tissue Distribution
  • Tomography, X-Ray Computed

Substances

  • Chelating Agents
  • Copper Radioisotopes
  • Integrin alphaVbeta3
  • Macrocyclic Compounds
  • Radioactive Tracers
  • Radiopharmaceuticals