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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

2.3K
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...
2.3K
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

1.7K
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...
1.7K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.0K
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...
2.0K
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

2.4K
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...
2.4K
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

1.9K
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...
1.9K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

1.8K
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...
1.8K

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Updated: May 24, 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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バクテリア媒介の細胞内根性ポリメリゼーション

Eleonora Ornati1,2, Jules Perrard1, Tobias A Hoffmann1

  • 1Department of Chemistry and Centre for Synthetic Biology, Technical University of Darmstadt, Peter-Grünberg-Str. 4, 64287 Darmstadt, Germany.

Journal of the American Chemical Society
|March 4, 2025
PubMed
まとめ

バクテリアの細胞は,原子移転基質ポリメリゼーションを用いて,その内部でポリマーを合成することができます. このバイオオートゴーナル法により 細胞に適合するポリマーが作られ 合成生物学と細胞工学の新たな道が開きます

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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Real-time Observation of the DNA Strand Exchange Reaction Mediated by Rad51
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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科学分野:

  • 合成生物学
  • ポリマー化学
  • 微生物学

背景:

  • 合成ポリマーの細胞内合成は困難です
  • バイオオートゴーナルポリメリゼーションはポリマー改造細胞への経路を提供します.
  • 細菌細胞は 活体ポリマーの工場として 存在します

研究 の 目的:

  • エシェリキア・コリ菌の細胞内リジカルポリメリゼーションを証明する
  • このポリメリゼーションプロセスの細胞互換性を調査する.
  • バクテリア細胞をバイオオートホーゴンなポリマー合成プラットフォームとして活用する.

主な方法:

  • バイオ分子によって誘発される原子移転基反応を用いたポリメリゼーションの開始.
  • NMR光学,GPC,および光ラベルによる細胞内ポリメリゼーションの確認.
  • 顕微鏡検査,フローサイトメトリー,代謝測定を用いた細胞の生存能力,行動,および膜の整合性の評価.

主要な成果:

  • エシェリキア・コライは 細胞内での様々なモノメアの ポリメリゼーションを成功裏に開始しました
  • 合成されたポリマーは細胞互換性があり,高い細胞活性を維持した.
  • 光染料はセルロースで合成されたポリマーに組み込まれました.

結論:

  • 細菌の細胞は ポリマー生産の生きた触媒として機能します
  • 細胞内原子移転ラジカルポリメリゼーションは 有効なバイオオートゴーナルツールです
  • このアプローチは 細胞工学や合成生物学の応用を 促進するものです