A combined spin trapping/EPR/mass spectrometry approach to study the formation of a cyclic peroxide by dienolic precursor autoxidation.

Org Biomol Chem

Université Aix-Marseille I-CNRS, UMR 6264: Laboratoire Chimie Provence, Spectrométries Appliquées à la Chimie Structurale, 13397 Marseille Cedex 20, France.

Published: March 2010

The spontaneous addition of air oxygen to a dienolic compound, yielding a cyclic peroxide, was followed by spin trapping (ST) combined with EPR spectroscopy and mass spectrometry (MS). Using two different nitrones, the ST/EPR study allowed the detection of the spin adduct of a radical intermediate, and the radical centre in the addend was identified after similar experiments performed with two different (13)C-labelled analogues of the substrate. The media were also submitted to electrospray ionisation, in both positive and negative modes, for structural characterisation of the spin adducts by tandem mass spectrometry. This allowed the structure of the hydroxylamine derivatives of the nitroxides formed to be identified. Following these results, a mechanism pathway was proposed for this autoxidation.

Download full-text PDF

Source
http://dx.doi.org/10.1039/b921694dDOI Listing

Publication Analysis

Top Keywords

cyclic peroxide
8
mass spectrometry
8
combined spin
4
spin trapping/epr/mass
4
trapping/epr/mass spectrometry
4
spectrometry approach
4
approach study
4
study formation
4
formation cyclic
4
peroxide dienolic
4

Similar Publications

Gold-Mercury-Platinum Alloy for Light-Enhanced Electrochemical Detection of Hydrogen Peroxide.

Sensors (Basel)

December 2024

Center for Experimental Chemistry Education of Shandong University, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.

In this study, a simple and easy synthesis strategy to realize the modification of AuHgPt nanoalloy materials on the surface of ITO glass at room temperature is presented. Gold nanoparticles as templates were obtained by electrochemical deposition, mercury was introduced as an intermediate to form an amalgam, and then a galvanic replacement reaction was utilized to successfully prepare gold-mercury-platinum (AuHgPt) nanoalloys. The obtained alloys were characterized by scanning electron microscopy, UV-Vis spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques.

View Article and Find Full Text PDF

Cytotoxic ROS-Consuming Mn(III) Synzymes: Structural Influence on Their Mechanism of Action.

Int J Mol Sci

December 2024

Department of Chemistry, Life Sciences and Environmental Sustainability, University of Parma, 43124 Parma, Italy.

ROS (i.e., reactive oxygen species) scavenging is a key function of various Mn-based enzymes, including superoxide dismutases (SODs) and catalases, which are actively linked to oxidative stress-related diseases.

View Article and Find Full Text PDF

Silk-engineered bioactive nanoparticles for targeted alleviation of acute inflammatory disease via macrophage reprogramming.

J Nanobiotechnology

January 2025

Integrative Science Center of Germplasm Creation in Western China (Chongqing) Science City, Biological Science Research Center, Southwest University, Chongqing, 400715, China.

Significant progress has been made in the development of potential therapies for diseases associated with inflammation and oxidative stress. Nevertheless, the availability of effective clinical treatments remains limited. Herein, we introduce a novel silk-based bioactive material, TPSF, developed by sequentially conjugating Tempol and phenylboronic acid pinacol ester to silk fibroin.

View Article and Find Full Text PDF

NPA7: A Dual Receptor Activating Peptide That Inhibits Cardiac Oxidative Stress.

Hypertension

January 2025

Cardiorenal Research Laboratory, Department of Cardiovascular Medicine, Mayo Clinic, Rochester, MN. (Xiaoyu Ma, J.C.M., D.G.M., Xiao Ma, Y.Z., S.P., Y.W., S.J.S., J.C.B.).

Background: Cardiomyocyte oxidative stress significantly contributes to the progression of hypertension-induced heart failure, highlighting the need for targeted therapies. We developed a novel peptide, NPA7, that coactivates the GC-A (guanylyl cyclase A)/cGMP and MasR (Mas receptor)/cAMP pathway. This study aimed to test NPA7's ability to inhibit oxidative stress by modulating the p62-KEAP1 (Kelch-like ECH-associated protein 1)-NRF2 (nuclear factor erythroid 2-related factor 2) pathway in human cardiomyocytes (HCMs) and a rat model of hypertension.

View Article and Find Full Text PDF

Superoxide dismutase (SOD) and Catalase (CAT) play a crucial role as the first line of defense antioxidant enzymes in a living cell. These enzymes neutralize the superoxide anion from the autooxidation of oxyhemoglobin (Oxy-Hb) and convert hydrogen peroxides into water and molecular oxygen. In this study, we fabricated hemoglobin submicron particles (HbMPs) using the Coprecipitation Crosslinking Dissolution (CCD) technique and incorporating first-line antioxidant enzymes (CAT, SOD) and second-line antioxidant (ascorbic acid, Vit.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!