Hydrolytic activity of new bioinspired MnIIIMnII and FeIIIMnII complexes as mimetics of PAPs: Biological and environmental interest

J Inorg Biochem. 2022 Nov:236:111965. doi: 10.1016/j.jinorgbio.2022.111965. Epub 2022 Aug 13.

Abstract

Coordination compounds that mimic Purple Acid Phosphatases (PAPs) have drawn attention in the bioinorganic field due to their capacity to cleave phosphodiester bonds. However, their catalytic activity upon phosphate triesters is still unexplored. Thus, we report the synthesis and characterization of two binuclear complexes, [MnIIMnIII(L1)(OAc)2]BF4 (1) and [MnIIFeIII(L1)(OAc)2]BF4 (2) (H2L1 = 2-[N,N-bis-(2- pyridilmethyl)aminomethyl]-4-methyl-6-[N-(2-hydroxy-3-formyl-5-methylbenzyl)-N-(2-pyridylmethyl)aminomethyl]phenol), their hydrolytic activity and antioxidant potential. The complexes were fully characterized, including the X-Ray diffraction (XRD) of 1. Density functional theory (DFT) calculations were performed to better understand their electronic and structural properties and phosphate conjugates. The catalytic activity was analyzed for two model substrates, a diester (BDNPP) and a triester phosphate (DEDNPP). The results suggest enhancement of the hydrolysis reaction by 170 to 1500 times, depending on the substrate and complex. It was possible to accompany the catalytic reaction of DEDNPP hydrolysis by phosphorus nuclear magnetic resonance (31P NMR), showing that both 1 and 2 are efficient catalysts. Moreover, we also addressed that 1 and 2 present a relevant antioxidant potential, protecting the yeast Saccharomyces cerevisiae, used as eukaryotic model of study, against the exposure of cells to acute oxidative stress.

Keywords: Antioxidant potential; Dinuclear Mn(II)-Fe(III) complex; Dinuclear Mn(II)-Mn(III) complex; Hydrolysis; Phosphate triester.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antioxidants* / pharmacology
  • Crystallography, X-Ray
  • Ferric Compounds* / chemistry
  • Hydrolysis
  • Phenols
  • Phosphates
  • Phosphorus

Substances

  • Antioxidants
  • Ferric Compounds
  • Phenols
  • Phosphates
  • Phosphorus