EPR Spectroscopy in Catalysis

2011 ◽  
pp. 1-39 ◽  
Author(s):  
Sabine Van Doorslaer ◽  
Damien M. Murphy
Keyword(s):  
Epr Spectroscopy

NMR and EPR Spectroscopy

1963 ◽  
Vol 36 (3_4) ◽  
pp. 247-248
Author(s):  
H. Dreeskamp
Keyword(s):  
Epr Spectroscopy

Properties of electrochemically generated primary cationradicals of phenyl- and 2-(4-tolyl)-1,3,4,7-tetramethylisoindoles

1980 ◽  
Vol 45 (6) ◽  
pp. 1669-1676 ◽  
Author(s):  
Pavel Kubáček
Keyword(s):  
Electrochemical Oxidation ◽  
Spin Polarization ◽  
High Spin ◽  
Epr Spectroscopy ◽  
Half Life ◽  
Electrochemical Behaviour ◽  
Epr Spectra ◽  
Electrochemical Generation ◽  
Splitting Constant ◽  
Reduced Temperature

The first step of electrochemical oxidation of 2-phenyl- and 2-(4-tolyl)-1,3,4,7-tetramethylisoindoles in anhydrous acetonitrile produces relatively stable cationradicals which have been studied by means of EPR spectroscopy using the method of internal electrochemical generation of radicals under reduced temperature. The same electrochemical behaviour of the both studied derivatives and identical EPR spectra of their cationradicals can be explained within the Huckel MO method. The largest contribution to the magnitude of splitting constant of nitrogen nucleus is due to π-σ-spin polarization of C-N bonds caused by high spin abundance of pz-AO of carbon atoms. Half-life of decomposition of the studied cationradicals is 4 min at -30°C.

Photoassisted Production of O2-• and H2 in Aqueous Medium Stimulated by Polythiophene in ZSM-5 Zeolite Channels

1999 ◽  
Vol 64 (1) ◽  
pp. 149-156 ◽  
Author(s):  
Gabriel Čík ◽  
František Šeršeň ◽  
Alena Bumbálová
Keyword(s):  
Reactive Oxygen Species ◽  
Ion Exchange ◽  
Visible Light ◽  
Aqueous Medium ◽  
Exchange Reaction ◽  
Epr Spectroscopy ◽  
Reactive Oxygen ◽  
Oxygen Species ◽  
Water Reduction ◽  
Ion Exchange Reaction

The formation of reactive oxygen species due to irradiation by a visible light of the polythiophene deposited in ZSM-5 zeolite channels in aqueous medium has been studied. Polymerization of thiophene was carried out in zeolite channels after the ion-exchange reaction of Na+ for Fe3+. By means of EPR spectroscopy, the temporarily generated 1O2 in irradiated aqueous medium was proved. The formation of O2-• was confirmed by the reduction of Fe3+-cytochrome c. Irradiation led to the water reduction to hydrogen.

scholarly journals Insights into the Antioxidant Mechanism of Newly Synthesized Benzoxazinic Nitrones: In Vitro and In Silico Studies with DPPH Model Radical

Antioxidants ◽  
2021 ◽  
Vol 10 (8) ◽  
pp. 1224
Author(s):  
Stefania Marano ◽  
Cristina Minnelli ◽  
Lorenzo Ripani ◽  
Massimo Marcaccio ◽  
Emiliano Laudadio ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Epr Spectroscopy ◽  
Point Of View ◽  
Uv Spectrophotometry ◽  
Design And Synthesis ◽  
Antioxidant Mechanism ◽  
Primary Mechanism ◽  
In Silico Studies ◽  
Wide Range

Synthetic nitrone spin-traps are being explored as therapeutic agents for the treatment of a wide range of oxidative stress-related pathologies, including but not limited to stroke, cancer, cardiovascular, and neurodegenerative diseases. In this context, increasing efforts are currently being made to the design and synthesis of new nitrone-based compounds with enhanced efficacy. The most researched nitrones are surely the ones related to α-phenyl-tert-butylnitrone (PBN) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) derivatives, which have shown to possess potent biological activity in many experimental animal models. However, more recently, nitrones with a benzoxazinic structure (3-aryl-2H-benzo[1,4]oxazin-N-oxides) have been demonstrated to have superior antioxidant activity compared to PBN. In this study, two new benzoxazinic nitrones bearing an electron-withdrawing methoxycarbonyl group on the benzo moiety (in para and meta positions respect to the nitronyl function) were synthesized. Their in vitro antioxidant activity was evaluated by two cellular-based assays (inhibition of AAPH-induced human erythrocyte hemolysis and cell death in human retinal pigmented epithelium (ARPE-19) cells) and a chemical approach by means of the α,α-diphenyl-β-picrylhydrazyl (DPPH) scavenging assay, using both electron paramagnetic resonance (EPR) spectroscopy and UV spectrophotometry. A computational approach was also used to investigate their potential primary mechanism of antioxidant action, as well as to rationalize the effect of functionalization on the nitrones reactivity toward DPPH, chosen as model radical in this study. Further insights were also gathered by exploring the nitrone electrochemical properties via cyclic voltammetry and by studying their kinetic behavior by means of EPR spectroscopy. Results showed that the introduction of an electron-withdrawing group in the phenyl moiety in the para position significantly increased the antioxidant capacity of benzoxazinic nitrones both in cell and cell-free systems. From the mechanistic point of view, the calculated results closely matched the experimental findings, strongly suggesting that the H-atom transfer (HAT) is likely to be the primary mechanism in the DPPH quenching.

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