Discriminative EPR Detection of NO and HNO by Encapsulated Nitronyl Nitroxides

Overview

Journal Free Radic Res

Publisher Informa Healthcare

Specialty Biochemistry

Date 2012 Nov 10

PMID 23136998

Citations 9

Authors

Andrey A Bobko

Alexander Ivanov

Valery V Khramtsov

Affiliations

Soon will be listed here.

Abstract

Nitric oxide, •NO, is one of the most important molecules in the biochemistry of living organisms. By contrast, nitroxyl, NO-, one-electron reduced analog of •NO which exists at physiological conditions in its protonated form, HNO, has been relatively overlooked. Recent data show that HNO might be produced endogenously and display unique biological effects. However, there is a lack of specific and quantitative methods of detection of endogenous HNO production. Here we present a new method for discriminative •NO and HNO detection by nitronyl nitroxides (NNs) using electron paramagnetic resonance (EPR). It was found that NNs react with •NO and HNO with similar rate constants of about 10(4) M(-1) s(-1) but yield different products: imino nitroxides and the hydroxylamine of imino nitroxides, correspondingly. An EPR approach for discriminative •NO and HNO detection using liposome-encapsulated NNs was developed. The membrane barrier of liposomes protects NNs against reduction in biological systems while is permeable to both analytes, •NO and HNO. The sensitivity of this approach for the detection of the rates of •NO/HNO generation is about 1 nM/s. The application of encapsulated NNs for real-time discriminative •NO/HNO detection might become a valuable tool in nitric oxide-related studies.

Citing Articles

The Chemistry of HNO: Mechanisms and Reaction Kinetics.

Michalski R, Smulik-Izydorczyk R, Pieta J, Rola M, Artelska A, Pierzchala K Front Chem. 2022; 10:930657.

PMID: 35864868 PMC: 9294461. DOI: 10.3389/fchem.2022.930657.

Azanone (HNO): generation, stabilization and detection.

Gallego C, Mazzeo A, Vargas P, Suarez S, Pellegrino J, Doctorovich F Chem Sci. 2021; 12(31):10410-10425.

PMID: 34447533 PMC: 8356739. DOI: 10.1039/d1sc02236a.

Kinetics of Azanone (HNO) Reactions with Thiols: Effect of pH.

Smulik-Izydorczyk R, Debowska K, Rostkowski M, Adamus J, Michalski R, Sikora A Cell Biochem Biophys. 2021; 79(4):845-856.

PMID: 33950351 PMC: 8558164. DOI: 10.1007/s12013-021-00986-x.

Pentacyanoferrate(II) complex of pyridine-4- and pyrazine-2-hydroxamic acid as source of HNO: investigation of anti-tubercular and vasodilation activities.

Muniz Carvalho E, de Freitas Paulo T, Saquet A, Abbadi B, Souza Macchi F, Bizarro C J Biol Inorg Chem. 2020; 25(6):887-901.

PMID: 32728907 DOI: 10.1007/s00775-020-01805-z.

A divergent mode of activation of a nitrosyl iron complex with unusual antiangiogenic activity.

Muniz Carvalho E, Ridnour L, Gouveia Junior F, Cabral P, Nascimento N, Wink D J Inorg Biochem. 2020; 210:111133.

PMID: 32619898 PMC: 8998159. DOI: 10.1016/j.jinorgbio.2020.111133.

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