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Related Concept Videos

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals01:17

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals

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Ideally, an unpaired electron shows a single peak in the EPR spectrum due to the transition between the two spin energy states. However, coupling interactions can occur between the spins of the unpaired electron and any neighboring spin-active nuclei. This hyperfine coupling results in hyperfine splitting, where the EPR signal is split into multiplets. The signals split into 2nI + 1 peaks, where n is the number of equivalent nuclei and I is the nuclear spin. These splitting patterns provide...
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

1.9K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
1.9K
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

4.1K
This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
4.1K
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

1.9K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
1.9K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.1K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.1K

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Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
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Electron Paramagnetic Resonance Tracks Condition-Sensitive Water Radical Cation.

Lei Li1, Qianbao Wu1, Shi-Kai Xiang2

  • 1Molecular Electrochemistry Laboratory, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China.

The Journal of Physical Chemistry Letters
|October 6, 2023
PubMed
Summary

Researchers identified a new way to track water radical cations (H2O+•) using electron paramagnetic resonance (EPR). This discovery offers insights into water redox chemistry and reactive oxygen species in various environments.

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Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
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Area of Science:

  • Chemistry
  • Environmental Science
  • Biology

Background:

  • Oxidizing species and radicals in water are crucial in catalysis, environmental processes, and biological systems.
  • Understanding reactive oxygen species and their formation pathways is essential for various scientific disciplines.

Purpose of the Study:

  • To present a novel, non-trapping chemical transformation pathway to track water radical cation (H2O+•) species.
  • To investigate the formation and reactivity of H2O+• under different environmental conditions.

Main Methods:

  • Utilized electron paramagnetic resonance (EPR) spectroscopy.
  • Employed a non-trapping chemical transformation pathway to detect H2O+•.
  • Investigated reactions of H2O+• with various trapping agents like DMPO, DMMP, MNP, BMPO, and PBN.

Main Results:

  • Demonstrated that H2O+• formation is sensitive to environmental conditions (light, mechanical action, gas/chemical introduction).
  • Revealed H2O+• oxidizes DMPO to an intermediate, which then reacts with hydroxyl radical (•OH) to form a detectable EPR signal.
  • Showed H2O+• reacts with other double-bond containing compounds (DMMP, MNP, BMPO, PBN) to form derivatives.

Conclusions:

  • H2O+• and •OH are ubiquitous in natural and experimental water systems.
  • The developed method provides a new perspective on understanding water redox chemistry.
  • This research contributes to the broader knowledge of reactive species in aqueous environments.