Optimizing PEG-Extended Apelin Analogues as Cardioprotective Drug Leads: Importance of the KFRR Motif and Aromatic Head Group for Improved Physiological Activity

J Med Chem. 2020 Oct 22;63(20):12073-12082. doi: 10.1021/acs.jmedchem.0c01395. Epub 2020 Oct 1.

Abstract

Apelin is an important contributor to the renin-angiotensin axis, regulating cardiovascular, metabolic, and neurological functions. Apelin-17 has especially potent cardio-physiological effects but is rapidly degraded in human blood (t0.5 ∼ 4 min). Angiotensin-converting enzyme 2 (ACE-2), neprilysin (NEP), and plasma kallikrein (KLKB1) cleave and inactivate it, with the latter cutting within the arginine-arginine site. Here, we show that analogues with an N-terminal polyethylene glycol (PEG) extension as well as peptide bond isosteres resist KLKB1 cleavage but that only the PEG-extended analogues significantly improve physiologically activity. The PEGylated analogues feature comparatively high log D7.4 values and high plasma protein binding, adding to their stability. An alanine scan of apelin-17 reveals that the integrity and conformational flexibility of the KFRR motif are necessary for cardio-physiological activity. An optimized Cbz-PEG6 analogue is presented that is stable in blood (t0.5 ∼ 18 h), has significant blood-pressure lowering effect, and shows fast recovery of heart function in Langendorff assay.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Apelin / analogs & derivatives
  • Apelin / chemistry*
  • Humans
  • Molecular Conformation
  • Polyethylene Glycols / chemistry*
  • Protective Agents / chemistry*
  • Stereoisomerism

Substances

  • Apelin
  • Protective Agents
  • Polyethylene Glycols

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