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Videos de Conceptos Relacionados

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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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 Formation: Addition00:47

Radical Formation: Addition

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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...
1.7K
Radical Formation: Overview01:03

Radical Formation: Overview

2.1K
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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Ribozymes02:47

Ribozymes

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The term ribozyme is used for RNA that can act as an enzyme. Ribozymes are mainly found in selected viruses, bacteria, plant organelles, and lower eukaryotes. Ribozymes were first discovered in 1982 when Tom Cech’s laboratory observed Group I introns acting as enzymes. This was shortly followed by the discovery of another ribozyme, Ribonulcease P, by Sid Altman’s laboratory. Both Cech and Altman received the Nobel Prize in chemistry in 1989 for their work on ribozymes.
Ribozymes can...
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Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

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This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
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Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
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Video Experimental Relacionado

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Monitoring Equilibrium Changes in RNA Structure by 'Peroxidative' and 'Oxidative' Hydroxyl Radical Footprinting
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Estructura de una ribonucleótido reductasa R2 radical de la proteína

Hugo Lebrette1,2, Vivek Srinivas1, Juliane John1

  • 1Department of Biochemistry and Biophysics, Stockholm University, Arrhenius Laboratories for Natural Sciences, Stockholm, Sweden.

Science (New York, N.Y.)
|October 5, 2023
PubMed
Resumen

Las ribonucleótidos reductasas aeróbicas (RNR) generan un radical en R2 para construir ADN. Una nueva estructura muestra cómo RNR protege y mueve este radical para la síntesis de ADN a través de la transferencia de electrones acoplados a protones (PCET).

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Área de la Ciencia:

  • La bioquímica
  • Biología estructural
  • Biología molecular

Sus antecedentes:

  • Las ribonucleótidos reductasas aeróbicas (RNR) son enzimas esenciales para la síntesis de ADN.
  • Los RNR generan un radical libre crítico en la subunidad R2 para la catálisis.
  • La transferencia radical a la subunidad R1 se produce a través de la transferencia de electrones acoplados a protones (PCET).

Objetivo del estudio:

  • Determinar la estructura de alta resolución del radical proteico de la clase Ie R2.
  • Aclarar el mecanismo de blindaje y translocación de radicales dentro de la RNR.
  • Comprender las bases estructurales de la transferencia de radicales durante el PCET.

Principales métodos:

  • Cristalografía en serie de femtosegundos con rayos X de electrones libres (XFEL-SFX) a temperatura ambiente.
  • Análisis estructural de alta resolución del radical proteico R2.

Principales resultados:

  • Reveló cambios conformacionales en R2 que protegen el radical.
  • Reorganizaciones estructurales identificadas que conectan el radical con la trayectoria de translocación.
  • Reestructuración observada de la red de enlaces de hidrógeno, incluido un enlace O-O corto (2,41 Å), que podría impedir la transferencia radical.

Conclusiones:

  • La estructura explica cómo RNR maneja y moviliza el radical para PCET.
  • Las ideas estructurales proporcionan una base para comprender los mecanismos de transferencia de radicales en las proteínas.
  • Los hallazgos tienen implicaciones para el campo más amplio de la química radical en los sistemas biológicos.