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Radical Chain-Growth Polymerization: Overview01:10

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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Radical Chain-Growth Polymerization: Mechanism01:09

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into...
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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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Radical Chain-Growth Polymerization: Chain Branching01:17

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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
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Once a ligand binds to a receptor, the signal is transmitted through the membrane and into the cytoplasm. The continuation of a signal in this manner is called signal transduction. Signal transduction only occurs with cell-surface receptors, which cannot interact with most components of the cell, such as DNA. Only internal receptors can interact directly with DNA in the nucleus to initiate protein synthesis. When a ligand binds to its receptor, conformational changes occur that affect the...
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Rab GTPases act in a regulated cascade during membrane fusion, helping the lipid bilayers mix. The Rab family of proteins are active when bound to GTP, and inactive when bound to GDP. Hence, they act as guanine nucleotide-dependent molecular switches. Rab-GTP recognizes and binds to long or short-range tethering proteins to capture the target vesicle. These tethers coordinate with SNAREs on the vesicle and the target membrane to assemble the trans SNARE complex that locks the mixing bilayers.
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Polimerización en cascada de cierre y apertura de anillo radical

Hanchu Huang1, Wenqi Wang1, Zefeng Zhou1

  • 1Department of Chemistry , Boston College , Chestnut Hill , Massachusetts 02467 , United States.

Journal of the American Chemical Society
|July 31, 2019
PubMed
Resumen
Este resumen es generado por máquina.

Los investigadores desarrollaron un nuevo método para sintetizar polímeros utilizando la polimerización en cascada de cierre y apertura de anillos radicales. Esta estrategia permite la creación de estructuras de polímeros complejos con capacidad de degradación incorporada.

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Área de la Ciencia:

  • Química de los polímeros
  • Síntesis orgánica

Sus antecedentes:

  • El desarrollo de nuevas estrategias de polimerización es crucial para la creación de materiales avanzados.
  • La polimerización radical ofrece vías versátiles para la síntesis de polímeros.

Objetivo del estudio:

  • Informar sobre una nueva estrategia para la síntesis de polímeros de la cadena principal a través de la polimerización en cascada de cierre y apertura de anillos radicales.
  • Permitir la síntesis de polímeros con estructuras de cadena principal complejas y funcionalidades degradables.

Principales métodos:

  • Optimización sistemática de las propiedades electrónicas de las estructuras de 1,6-dieno para una eficiente ciclo polimerización de radicales.
  • Fusión de 1,6-dieno con sulfuro de alilo o motivos de sulfona de alilo para iniciar las reacciones en cascada.
  • Utilizando la extrusión de SO2 a partir de sulfona alilica fusionada con 1,6-dieno para generar un radical alquilo propagador con desactivación reversible.

Principales resultados:

  • Se ha logrado una eficiente ciclo polimerización de radicales a través de estructuras optimizadas de 1,6-dieno.
  • Se ha demostrado una reacción en cascada de cierre y apertura de anillos impulsada por la polimerización de grandes monómeros macrocíclicos.
  • Se ha generado con éxito un radical alquilo propagable capaz de desactivación reversible.

Conclusiones:

  • La estrategia presentada proporciona una plataforma general para la síntesis de polímeros con arquitecturas complejas de cadena principal.
  • Este método permite la incorporación de funcionalidades degradables en las cadenas principales de polímeros.
  • La polimerización en cascada de cierre y apertura de anillos radicales ofrece un enfoque poderoso para el diseño de polímeros avanzados.