Antioxidant Hydrogen-Atom-Transfer to DPPH Radicals by Hybrids of {Hyaluronic-Acid Components}@SiO2

Langmuir. 2022 Oct 11;38(40):12333-12345. doi: 10.1021/acs.langmuir.2c02021. Epub 2022 Sep 27.

Abstract

Hydrogen-atom-transfer (HAT) is among the key mechanisms of antioxidant and antiradical activity in natural systems. Hyaluronic acid (HyA) is currently used extensively in health and cosmetics applications. Herein it is shown that {HyA@SiO2} hybrids based on hyaluronic acid (HyA) components grafted on SiO2 nanoparticles enable significant HAT activity versus DPPH radicals, while the homogeneous HyA counterparts are practically inactive. The {HyA@SiO2} hybrids consist of the two building blocks of HyA [d-glucuronic acid (GLA) and N-acetyl-d-glucosamine (GLAM)] covalently grafted on SiO2 nanoparticles. Based on the kinetic-thermodynamic Arrhenius study, we show that the {SiO2@GLA} hybrids operate spontaneously via hydrogen-atom-transfer (HAT) with a low activation energy barrier, i.e., by ΔΕα ∼ 20 kJ/mol vs the nongrafted counterparts. Moreover, a doubly grafted {GLA@SiO2@GLAM} nanohybrid, i.e. that contains both components of HyA, shows the most significant antioxidant activity. FTIR and Raman analysis reveal that local H-bonding between the SiO2 matrix, GLA, and GLAM in {GLA@SiO2@GLAM} decreases the activation barrier of the HAT mechanism. Thus, {GLA@SiO2@GLAM} nanohybrids exemplify a novel family of materials that are not the mere sum of their components. The present case is the first example of non-phenolic molecules being able to perform antiradical HAT, opening new perspectives not foreseen until today.

Publication types

  • Case Reports
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetylglucosamine
  • Antioxidants / chemistry
  • Antioxidants / pharmacology
  • Glucuronic Acid
  • Humans
  • Hyaluronic Acid* / chemistry
  • Hydrogen* / chemistry
  • Silicon Dioxide

Substances

  • Antioxidants
  • Silicon Dioxide
  • Hydrogen
  • Glucuronic Acid
  • Hyaluronic Acid
  • Acetylglucosamine