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Related Concept Videos

Radical Formation: Overview01:03

Radical Formation: Overview

2.7K
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...
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

3.0K
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...
3.0K
Radical Formation: Homolysis00:54

Radical Formation: Homolysis

4.6K
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
4.6K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

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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...
2.8K
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

2.6K
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...
2.6K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

2.6K
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...
2.6K

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Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR
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Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR

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Dynamic nuclear polarization in solid samples by electrical-discharge-induced radicals.

Itai Katz1, Aharon Blank1

  • 1Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa 32000, Israel.

Journal of Magnetic Resonance (San Diego, Calif. : 1997)
|November 8, 2015
PubMed
Summary
This summary is machine-generated.

This study demonstrates a new method for Dynamic Nuclear Polarization (DNP) signal enhancement in solid samples. Electrical discharges generate surface radicals, eliminating the need for solvents and exogenous radicals in Nuclear Magnetic Resonance (NMR).

Keywords:
DNPDynamic nuclear polarizationMetabolic MRINMRSurface NMR

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Area of Science:

  • Nuclear Magnetic Resonance (NMR) Spectroscopy
  • Solid-State Chemistry
  • Medical Applications

Background:

  • Dynamic Nuclear Polarization (DNP) enhances Nuclear Magnetic Resonance (NMR) signals.
  • Traditional DNP methods rely on exogenous radicals in solution.
  • Exogenous radicals can pose regulatory challenges for medical applications.

Purpose of the Study:

  • To develop a solvent-free DNP method for solid samples.
  • To generate radicals in situ on the sample surface.
  • To explore applications in medical imaging and analytical NMR.

Main Methods:

  • Utilizing electrical discharges to generate radicals on the surface of solid samples.
  • Applying these surface radicals for proton DNP signal enhancement.
  • Investigating the stability and properties of the generated radicals.

Main Results:

  • Achieved significant proton DNP signal enhancements in solid samples without solvents or exogenous radicals.
  • Generated radicals are stable under moderate vacuum but readily annihilate upon dissolution or air exposure.
  • Demonstrated the potential for solvent-free DNP in medical and analytical applications.

Conclusions:

  • A novel, solvent-free DNP approach using surface-generated radicals is presented.
  • This method overcomes limitations of traditional DNP, particularly for solvent-intolerant samples.
  • The technique shows promise for regulatory-friendly medical applications and specialized analytical NMR.