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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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 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 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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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 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 Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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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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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Potenciales de redox de las bacterias polimerización radical controlada

Mitchell D Nothling1, Hanwei Cao2, Thomas G McKenzie1

  • 1Department of Chemical Engineering, University of Melbourne, Melbourne, VIC 3010, Australia.

Journal of the American Chemical Society
|December 29, 2020
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Resumen
Este resumen es generado por máquina.

Las bacterias

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Área de la Ciencia:

  • Microbiología
  • Química de los polímeros
  • Biología sintética

Sus antecedentes:

  • Las bacterias utilizan intrincados sistemas de transporte de electrones para obtener energía, liberando electrones extracelulares.
  • La proliferación bacteriana causa una caída en el potencial redox (Eh) influenciado por factores microbianos.

Objetivo del estudio:

  • Para aprovechar el poder de reducción bacteriana para la producción de radicales abióticos.
  • Desarrollar una síntesis molecular bioortogonal utilizando el eflujo de electrones bacterianos.

Principales métodos:

  • Utilizó Escherichia coli y Salmonella enterica como organismos modelo.
  • Intervenido en el flujo de electrones respiratorios terminales de las bacterias con una sal de aryldiazonium.
  • Se ha iniciado la polimerización de radicales controlados bioortogonales mediante transferencia de cadena de fragmentación por adición reversible (BacRAFT).

Principales resultados:

  • Producción demostrada de radicales abióticos mediada por el metabolismo bacteriano y las lanzaderas redox activas.
  • Se logró la polimerización radical controlada, dando lugar a matrices extracelulares sintéticas.
  • Polímeros de vinilo sintetizados con pesos moleculares definidos y baja dispersión.

Conclusiones:

  • El poder de reducción bacteriana puede ser subvertido para la síntesis molecular dirigida.
  • Este método permite la creación de materiales vivos de ingeniería.
  • Ofrece nuevas posibilidades para el diseño de materiales adaptativos y auto-regenerativos.