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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.3K
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: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.3K
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...
2.3K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

2.1K
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...
2.1K
Radical Formation: Overview01:03

Radical Formation: Overview

2.3K
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...
2.3K
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

2.2K
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...
2.2K
Radical Formation: Elimination00:51

Radical Formation: Elimination

2.0K
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...
2.0K

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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
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Probing enzymatic activity - a radical approach.

Neil C Taylor1, Gary Hessman1, Holger B Kramer2

  • 1School of Chemistry, Trinity College Dublin, Trinity Biomedical Sciences Institute 152-160 Pearse St. Dublin 2 Ireland jmcgoura@tcd.ie.

Chemical Science
|June 14, 2021
PubMed
Summary
This summary is machine-generated.

Researchers developed novel latent ubiquitin-based probes to study deubiquitinating enzymes (DUBs). These probes utilize a photoinitiated radical mechanism, offering precise control and targeting DUBs via active site cysteines for improved disease research.

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Area of Science:

  • Biochemistry
  • Chemical Biology
  • Enzymology

Background:

  • Deubiquitinating enzymes (DUBs) are crucial in the ubiquitin cascade.
  • DUB dysregulation is linked to diseases like cancer and neurodegeneration.
  • Activity-based probes are vital tools for studying DUBs.

Purpose of the Study:

  • To develop novel latent ubiquitin-based probes for DUBs.
  • To explore a site-selective, photoinitiated radical mechanism for DUB targeting.
  • To overcome limitations of existing nucleophilic and photocrosslinking probes.

Main Methods:

  • Development of latent ubiquitin-based probes with an inert alkene warhead.
  • Utilizing a photoinitiated radical mechanism for probe activation.
  • Testing probe reactivity against recombinant DUBs and endogenous DUBs in cell lysate.

Main Results:

  • Demonstrated successful targeting of DUBs via a photoinitiated radical mechanism.
  • Showcased probe inertness under ambient conditions, enabling controlled reactions.
  • Validated probe efficacy in capturing endogenous DUB activity from cell lysates.
  • Highlighted the requirement of a free active site cysteine for probe interaction.

Conclusions:

  • The developed probes offer a new strategy for studying DUBs.
  • This approach provides temporal control over enzyme-probe interactions.
  • Enables more finely resolved investigations into DUB function and dysregulation in disease contexts.