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Updated: Jul 4, 2025

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

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ENDOR光谱揭示了SAM酶活性部位中的"自由"5'-脱氧基实际上是与胺结合的4Fe-4S集群的密切相互作用

Hao Yang1, Madeline B Ho1, Maike N Lundahl2

  • 1Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.

Journal of the American Chemical Society
|February 3, 2024
PubMed
概括

这项研究揭示了酸盐激酶激活酶中的5'-脱氧腺 (5'-dAdo•) 基与4Fe-4S集群密切相互作用. 这种涉及异常合的相互作用,

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Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals01:17

Electron Paramagnetic Resonance (EPR) Spectroscopy: Organic Radicals

Ideally, an unpaired electron shows a single peak in the EPR spectrum due to the transition between the two spin energy states. However, coupling interactions can occur between the spins of the unpaired electron and any neighboring spin-active nuclei. This hyperfine coupling results in hyperfine splitting, where the EPR signal is split into multiplets. The signals split into 2nI + 1 peaks, where n is the number of equivalent nuclei and I is the nuclear spin. These splitting patterns provide...
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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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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...
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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:
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Radical Reactivity: Electrophilic Radicals

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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