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Radical Formation: Abstraction00:47

Radical Formation: Abstraction

The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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 molecule. These three...
Radical Formation: Overview01:03

Radical Formation: Overview

A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the latter, also known...
Radical Formation: Addition00:47

Radical Formation: Addition

Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an unpaired...
Radical Formation: Elimination00:51

Radical Formation: Elimination

Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...
Mass Spectrometry: Molecular Fragmentation Overview01:20

Mass Spectrometry: Molecular Fragmentation Overview

The ionization of a molecule into a molecular ion inside the mass spectrometer causes instability in the molecule's structure due to the loss of an electron. This eventually leads to the fragmentation or breaking of some bonds in the molecule. The fragmentation occurs predominantly at specific bonds to yield relatively stable fragments.
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...

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Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
08:22

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization

Published on: August 6, 2018

電子捕獲解離における根本変換と遷移.

Benjamin N Moore1, Tony Ly, Ryan R Julian

  • 1Department of Chemistry, University of California, Riverside, California 92521, USA.

Journal of the American Chemical Society
|April 19, 2011
PubMed
まとめ

電子捕捉解離 (ECD) はプロテオミクス技術である. 新しい発見は,水素欠乏の急性化学がECDの断片化に大きく寄与し,新しい力学的洞察を提供することを示唆しています.

科学分野:

  • プロテオミクスと分析化学

背景:

  • 電子捕捉解離 (ECD) はプロテオミクスにとって不可欠であり,配列と改変分析に役立ちます.
  • ECDの断片化を誘発する正確な化学的メカニズムについては,依然として議論されている.
  • 既存の研究は,しばしば,脊椎以外の解離経路を無視している.

研究 の 目的:

  • ECDメカニズムにおけるサイドチェーン損失および他の解離チャネルの役割を調査する.
  • ECDにおける初期根幹形成の後の化学的経路を探求する.
  • 水素欠乏の基質化学がECDの断片化パターンを影響するかどうかを判断する.

主な方法:

  • ECDにおけるサイドチェーン喪失と代替解離経路に焦点を当てています.
  • ECDによって生成された断片イオンを分析する.
  • ECDの観測を,既知の水素欠乏の基質化学と比較する.

主要な成果:

  • ECDで最初に形成された水素に富んだラジカルは,素早く水素不足のラジカルに変換されます.
  • その後の解離は,主に,この水素欠乏の基質化学によって媒介されます.
  • ECD断片の統計的分析は,水素欠乏の過激化学の予測と一致しています.
  • 水素欠乏の基質化学は,二硫化結合における選択的解離を説明する.

さらに関連する動画

Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
10:34

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

Published on: April 24, 2014

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers
08:51

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

Published on: August 18, 2017

関連する実験動画

Last Updated: Jun 2, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
08:22

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization

Published on: August 6, 2018

Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow
10:34

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

Published on: April 24, 2014

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers
08:51

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

Published on: August 18, 2017

結論:

  • 水素欠乏の基質化学は,ECDの断片化において,極めて重要で,しばしば見過ごされている役割を果たします.
  • ECDメカニズムは,水素欠乏の根幹経路を考慮することによって,よりよく理解することができます.
  • 発見は,水素欠乏ラジカルを生成するための独立した非ECD方法を使用して再現可能です.