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相关概念视频

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

在电子捕获解离过程中,激素的转换和迁移.

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
概括

电子捕获解离 (ECD) 是一种蛋白质组学技术. 新的发现表明,缺乏的激素化学显著促进了ECD碎片化,提供了新的机制性见解.

科学领域:

  • 蛋白质组学和分析化学

背景情况:

  • 电子捕获解离 (ECD) 对蛋白质组学至关重要,有助于序列和修饰分析.
  • 正确的化学机制驱动ECD碎片化仍在争论中.
  • 现有的研究往往忽略了非脊柱分离途径.

研究的目的:

  • 调查侧链损失和其他解离通道在ECD机制中的作用.
  • 探索在ECD中初始激素形成后的化学途径.
  • 为了确定缺少的激素化学是否会影响ECD碎片化模式.

主要方法:

  • 专注于ECD的侧链损失和替代解离途径.
  • 分析通过ECD产生的碎片离子.
  • 将ECD观测与已知的缺水激素化学进行比较.

主要成果:

  • 最初在ECD中形成的富含的基因迅速转化为缺乏的基因.
  • 随后的解离主要由这种缺的激素化学物质介导.
  • 对ECD碎片的统计分析与缺激素化学的预测一致.
  • 缺乏的激素化学解释了二硫化物键的选择性解离.

结论:

  • 缺乏的激素化学在ECD碎片化中起着至关重要的,但经常被忽视的作用.

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Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
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10:34

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

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Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

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  • 通过考虑缺基路径,可以更好地理解ECD机制.
  • 通过使用独立的非ECD方法来产生缺基的研究结果是可复制的.