Tri-Manganese(III) Salen-Based Cryptands: A Metal Cooperative Antioxidant Strategy that Overcomes Ischemic Stroke Damage In Vivo

J Am Chem Soc. 2020 Jun 3;142(22):10219-10227. doi: 10.1021/jacs.0c03805. Epub 2020 May 26.

Abstract

Oxidative stress is one of the hallmarks of ischemic stroke. Catalase-based (CAT) biomimetic complexes are emerging as promising therapeutic candidates that are expected to act as neuroprotectants for ischemic stroke by decreasing the damaging effects from H2O2. Unfortunately, these molecules result in the unwanted production of the harmful hydroxyl radical, HO. Here, we report a series of salen-based tri-manganese (Mn(III)) metallocryptands (1-3) that function as catalase biomimetics. These cage-like molecules contain a unique "active site" with three Mn centers in close proximity, an arrangement designed to facilitate metal cooperativity for the effective dismutation of H2O2 with minimal HO production. In fact, significantly greater oxygen production is seen for 1-3 as compared to the monomeric Mn(Salen) complex, 1c. The most promising system, 1, was studied in further detail and found to confer a greater therapeutic benefit both in vitro and in vivo than the monomeric control system, 1c, as evident from inter alia studies involving a rat model of ischemic stroke damage and supporting histological analyses. We thus believe that metallocryptand 1 and its analogues represent a new and seemingly promising strategy for treating oxidative stress related disorders.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Antioxidants / chemical synthesis
  • Antioxidants / chemistry
  • Antioxidants / pharmacology*
  • Apoptosis / drug effects
  • Brain Ischemia / drug therapy*
  • Brain Ischemia / metabolism
  • Brain Ischemia / pathology
  • Catalase / metabolism
  • Cells, Cultured
  • Coordination Complexes / chemical synthesis
  • Coordination Complexes / chemistry
  • Coordination Complexes / pharmacology*
  • Disease Models, Animal
  • Ethylenediamines / chemistry
  • Ethylenediamines / pharmacology
  • Humans
  • Ischemic Stroke / drug therapy*
  • Ischemic Stroke / metabolism
  • Ischemic Stroke / pathology
  • Male
  • Manganese / chemistry
  • Manganese / pharmacology
  • Molecular Conformation
  • Neuroprotective Agents / chemical synthesis
  • Neuroprotective Agents / chemistry
  • Neuroprotective Agents / pharmacology*
  • Optical Imaging
  • Oxygen / metabolism
  • Rats
  • Rats, Sprague-Dawley

Substances

  • Antioxidants
  • Coordination Complexes
  • Ethylenediamines
  • Neuroprotective Agents
  • Manganese
  • disalicylaldehyde ethylenediamine
  • Catalase
  • Oxygen