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Radical Formation: Homolysis00:54

Radical Formation: Homolysis

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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.
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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

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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: Steric Effects01:10

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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...
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Radical Formation: Abstraction00:47

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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.
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Radical Reactivity: Electrophilic Radicals01:02

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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...
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Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR
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Hyperpolarized water through dissolution dynamic nuclear polarization with UV-generated radicals.

Arthur C Pinon1, Andrea Capozzi1, Jan Henrik Ardenkjær-Larsen2

  • 1Center for Hyperpolarization in Magnetic Resonance, Department of Health Technology, Technical University of Denmark, Building 349, 2800, Kgs Lyngby, Denmark.

Communications Chemistry
|January 27, 2023
PubMed
Summary

This study introduces a new way to hyperpolarize water protons using UV light to generate radicals. Traditional methods struggle with rapid relaxation caused by radicals, but this approach reduces that effect. The researchers achieved high polarization levels in water and demonstrated the method's potential by acquiring a nitrogen spectrum from urea. These results suggest the technique could be useful in MRI and NMR studies. The method may offer an alternative to current contrast agents used in imaging. The findings support further development of this dDNP technique for clinical and research applications.

Keywords:
dissolution DNPhyperpolarized water MRIUV-generated radicalsNMR spectroscopy

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Area of Science:

  • Magnetic resonance imaging (MRI) development
  • Nuclear magnetic resonance (NMR) spectroscopy
  • Dynamic nuclear polarization (DNP) techniques

Background:

Hyperpolarized water has emerged as a promising alternative to traditional contrast agents in MRI. Conventional methods rely on gadolinium-based compounds, which have limitations in tracking biochemical processes. While hyperpolarized water could provide insights into proton exchange and chemical reactions, achieving stable polarization remains a challenge. Radicals are essential for DNP, but they also cause rapid relaxation of the polarized state. Prior research has shown that water protons can be hyperpolarized, but maintaining this state during transfer is difficult. This gap motivated researchers to explore alternative radical generation methods. UV-generated radicals offer a new approach to dDNP. That uncertainty drove the development of this novel technique. No prior work had resolved the issue of radical-induced relaxation during transfer. This study addresses that limitation.

Purpose Of The Study:

The aim of this study is to demonstrate a novel dDNP method using UV-generated radicals for hyperpolarizing water protons. The specific problem is the rapid relaxation caused by radicals during transfer to NMR or MRI systems. The motivation is to improve the feasibility of hyperpolarized water for clinical and research applications. By using UV-generated radicals, the researchers aim to reduce relaxation effects. This approach could enhance the stability of hyperpolarized states during transfer. The study also seeks to validate the method by acquiring a nitrogen spectrum from urea. This validation confirms magnetization transfer from water to nitrogen nuclei. The researchers propose that this method could expand the use of hyperpolarized water in MRI.

Main Methods:

The study employs dissolution Dynamic Nuclear Polarization (dDNP) with UV-generated radicals. Pure water samples were used to achieve hyperpolarization. UV light was applied to generate labile radicals in situ. These radicals facilitated the polarization of water protons. The dissolution process was carefully controlled to minimize relaxation. A single scan was used to acquire a 15N spectrum from urea. The magnetization transfer from water to nitrogen nuclei was spontaneous. The method was tested under conditions mimicking clinical and research settings.

Main Results:

The researchers achieved water proton magnetizations equivalent to a 10,000 T field at room temperature. This level of polarization was obtained using UV-generated radicals. The radicals were labile, which reduced their impact on relaxation. A 15N spectrum from natural abundance urea was successfully acquired. The spectrum was obtained with a single scan, demonstrating efficiency. The magnetization transfer from water to nitrogen nuclei was spontaneous. These results suggest the method's potential for NMR and MRI applications. The findings support the use of UV-generated radicals in dDNP.

Conclusions:

The authors propose that UV-generated radicals can effectively hyperpolarize water protons. This method reduces radical-induced relaxation during transfer. The study demonstrates the feasibility of this approach in practice. The acquired 15N spectrum confirms magnetization transfer. These results suggest the method could be useful in MRI and NMR studies. The researchers suggest that this technique may provide an alternative to Gd-based contrast agents. The findings may support further development of dDNP for clinical use. The authors suggest that this method could expand the applications of hyperpolarized water.

This method uses UV light to generate labile radicals in situ, reducing relaxation effects during transfer.

It confirms spontaneous magnetization transfer from water protons to nitrogen nuclei in a single scan.

Radicals cause rapid relaxation of hyperpolarized states, limiting their usefulness in MRI and NMR.

Dissolution enables transfer of hyperpolarized water to the NMR or MRI system while preserving polarization.

Water protons reached magnetizations equivalent to a 10,000 T field at room temperature.

The method may provide an alternative to Gd-based contrast agents for angiographic and perfusion MRI.