Rapid Photoactivated Generation of Nitroxyl (HNO) under Neutral pH Conditions

Yang Zhou; Ruth B Cink; Rohan S Dassanayake; Alexander J Seed; Nicola E Brasch; Paul Sampson

doi:10.1002/anie.201605160

Rapid Photoactivated Generation of Nitroxyl (HNO) under Neutral pH Conditions

Angew Chem Int Ed Engl. 2016 Oct 10;55(42):13229-13232. doi: 10.1002/anie.201605160.

Authors

Yang Zhou¹, Ruth B Cink², Rohan S Dassanayake¹, Alexander J Seed¹, Nicola E Brasch³, Paul Sampson⁴

Affiliations

¹ Department of Chemistry and Biochemistry, Kent State University (KSU), Kent, OH, 44240, USA.
² School of Applied Sciences, Auckland University of Technology (AUT), Private Bag 92006, Auckland, 1142, New Zealand.
³ School of Applied Sciences, Auckland University of Technology (AUT), Private Bag 92006, Auckland, 1142, New Zealand. nbrasch@aut.ac.nz.
⁴ Department of Chemistry and Biochemistry, Kent State University (KSU), Kent, OH, 44240, USA. psampson@kent.edu.

PMID: 27633899
DOI: 10.1002/anie.201605160

Abstract

Directly obtaining kinetic and mechanistic data for the reactions of nitroxyl (HNO) with biomolecules (k≈10³ -10⁷ m^-1 s^-1 ) is not feasible for many systems because of slow HNO release from HNO donor molecules (t_1/2 is typically minutes to hours). To address this limitation, we have developed a photoactivatable HNO donor incorporating the (3-hydroxy-2-naphthalenyl)methyl phototrigger, which rapidly releases HNO on demand. A "proof of concept" study is reported, which demonstrates that, upon continuous xenon light excitation, rapid decomposition of the HNO donor occurs within seconds. The amount of HNO generated is strongly dependent on solvent and the rate of the reaction is dependent on the light intensity.

Keywords: HNO donors; nitrosyl hydride; nitroxyl; photochemistry; photolysis.

Publication types

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