ESR study of the mechanism of radical formation during liquid-and solid-phase radiolyses of ethylamines

Belevskii, V. N.; Belopushkin, S. I.; Nuzhdin, Kirill B.

doi:10.1134/s0018143907010031

Cited by 9 publications

(12 citation statements)

References 18 publications

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“…To detect the electrogenerated cation radical species (DCHA •+ ), a reactive intermediate formed after the electro-oxidation of DCHA, ESR experiments were performed using 5 × 10 –3 M DCHA in O 2 -saturated 0.1 M PBS (pH 10.5) before and after the prolonged electrolysis reaction at 1.0 V, as shown in Figure . The experimental ESR spectrum has a g -value of 2.0083 and consists of three most intense and sharp lines of equal intensity (1:1:1) with a splitting of ∼16 G, which is because of the free electron generated on the nitrogen nuclei N (1 N, I = 1). , Further, each of these three lines split into a doublet, which is due to the interaction of the unpaired electron with the α- 1 H (N–H, I = 1/2). The less-intense three lines are due to the presence of two equivalent (CH) protons, as can be seen in the structure of DCHA •+ attached to the nitrogen nucleus, Figure S11.…”

Section: Resultsmentioning

confidence: 99%

“…The experimental ESR spectrum has a g-value of 2.0083 and consists of three most intense and sharp lines of equal intensity (1:1:1) with a splitting of ∼16 G, which is because of the free electron generated on the nitrogen nuclei N 14 (1 N, I = 1). 31,32 Further, each of these three lines split into a doublet, which is due to the interaction of the unpaired electron with the α-1 H (N−H, I = 1/2). The less-intense three lines are due to the presence of two equivalent (CH) protons, as can be seen in the structure of DCHA •+ attached to the nitrogen nucleus, Figure S11.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Bimodal Electrogenerated Chemiluminescence of the Luminol/Dicyclohexylamine (DCHA) System: A Novel and Highly Sensitive Detection of DCHA via ECL-Flow Injection Analysis

Sornambigai

Raju

2021

Anal. Chem.

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Though luminol is one of the most prominent and extensively studied luminophores in ECL studies, only H2O2 has been widely used as a co-reactant. This limits the variety of applications because of the short-time radical stability and low quantum efficiency. In the present work, we identified dicyclohexylamine (DCHA) as a new and highly efficient anodic co-reactant in ECL for the luminol molecule. The electrochemical and ECL behavior of the luminol/DCHA system was studied on a simple bare GCE surface, which results in two anodic ECL peaks at the potential region of +0.38 and +0.94 V vs Ag/AgCl. The evidence of (DCHA•+) and O2 •– generated in the system was detected via flat-cell electron spin resonance (ESR) spectroscopy experiments at ∼20 °C. Using the bimodal ECL system, the highly sensitive detection of luminol was achieved with the detection limit down to 1.5 pM. Further, a homebuilt electrochemiluminescent detector coupled with a flow injection analysis (ECL-FIA) system was adopted to detect the DCHA contaminant in harvested honey, which achieved higher detection and sensitivity under the optimized experimental conditions. DCHA was detected in the range of 10 nM to 100 μM with the detection limit of 2 nM (S/N = 3). The present findings of new luminol/DCHA ECL signals produced a strong ECL emission, which leads to a greater potential to meet the fast-developing analytical application of a luminol-based ECL system.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Bimodal Electrogenerated Chemiluminescence of the Luminol/Dicyclohexylamine (DCHA) System: A Novel and Highly Sensitive Detection of DCHA via ECL-Flow Injection Analysis

Sornambigai

Raju

2021

Anal. Chem.

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“…11) It should be mentioned that a primary photochemical process is the electron transfer from the singlet excited molecule of an amine to a chlorocarbon molecule in the excited CTC (Belevskii et al, 2007;Boszczyk & Latowski, 1989).…”

Section: Ii-formation Of a Charge Transfer Complexmentioning

confidence: 99%

“…Also, excited states of aromatic molecules are expected to be involved in charge transfer interactions with chlorobenzene through exciplex formation. Therefore, the electronic excitation of the electron donor molecule in the presence of chlorobenzene is expected to accompany the process of electron transfer to the chlorobenzene molecule (Belevskii, Belopushkin, & Nuzhdin, 2007).…”

Section: Introductionmentioning

confidence: 99%

“…Such studies explained the fluorescence quenching by electron transfer mechanism. It was reported that fluorescence quenching of carbazole by CCl 4 , is accompanied by a photochemical reaction (Belevskii et al, 2007). Moreover, the fluorescence quenching of aniline and its derivatives by the chloromethanes was ascertained (Apatoff & Norwitz, 1973;Kumagai, 1962).…”

Section: Introductionmentioning

confidence: 99%

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ɤ-Radiation-induced N-phenylation of aniline using chlorobenzene: a novel route for diphenylamine formation

Sife-Eldeen

2020

Journal of Radiation Research and Applied Sciences

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A novel route of diphenylamine (DPA) formation via ɤ-radiation-induced N-phenylation of aniline by chlorobenzene in oxygen-free condition is reported. A capillary gas chromatography-mass spectrometry method was developed for DPA identification and quantification. The effects of the reactants molar ratio, absorbed radiation dose, and dose rate on the yield of DPA were investigated in ɤ-irradiated aniline/chlorobenzene samples. The yield of DPA was found to be maximum at aniline: chlorobenzene molar ratio of about 1:1. Generally, the yield of DPA increases as absorbed dose increases. The G (DPA) was determined to be 11.6 μM/J. The DPA yield was found to increase linearly as dose rate increases. This observation can be attributed to the formation of DPA via spur reactions. A reaction mechanism was suggested for the DPA formation in the ɤ-irradiated aniline/chlorobenzene samples.

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Application of Optically Detected EPR to Study the Stability of Sterically Hindered Amine Radical Cations to Proton Transfer Reaction

2009

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ESR study of the mechanism of radical formation during liquid-and solid-phase radiolyses of ethylamines

Cited by 9 publications

References 18 publications

Bimodal Electrogenerated Chemiluminescence of the Luminol/Dicyclohexylamine (DCHA) System: A Novel and Highly Sensitive Detection of DCHA via ECL-Flow Injection Analysis

Bimodal Electrogenerated Chemiluminescence of the Luminol/Dicyclohexylamine (DCHA) System: A Novel and Highly Sensitive Detection of DCHA via ECL-Flow Injection Analysis

ɤ-Radiation-induced N-phenylation of aniline using chlorobenzene: a novel route for diphenylamine formation

Application of Optically Detected EPR to Study the Stability of Sterically Hindered Amine Radical Cations to Proton Transfer Reaction

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