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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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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...
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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Step-Growth Polymerization: Overview01:03

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Enzymatic Reaction Network-Driven Polymerization-Induced Transient Coacervation.

Surbhi Sharma1, Andrea Belluati2, Mohit Kumar1

  • 1Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, Mainz, 55122, Germany.

Angewandte Chemie (International Ed. in English)
|December 10, 2024
PubMed
Summary
This summary is machine-generated.

Researchers developed an enzyme-driven system for controlled ATP-fueled coacervation, mimicking cellular processes. This enzymatic reaction network (ERN) enables adjustable dynamics for biomimetic applications and artificial cell development.

Keywords:
ATPBioATRPCoacervatesEnzymatic Reaction NetworkLiquid-liquid phase separation

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Area of Science:

  • Biomimetic chemistry
  • Synthetic biology
  • Polymer chemistry

Background:

  • Living cells exhibit complex microenvironments with highly accurate and efficient enzyme-driven processes.
  • Achieving comparable in vitro control over such dynamic processes remains a challenge.

Purpose of the Study:

  • To design an enzymatic reaction network (ERN) that combines antagonistic and orthogonal enzymatic networks.
  • To achieve adjustable dynamics of ATP-fueled transient coacervation.
  • To explore enzymatic control over coacervation and dissolution for biomimetic applications.

Main Methods:

  • Synthesized poly(dimethylaminoethyl methacrylate) via horseradish peroxidase (HRP)-mediated Biocatalytic Atom Transfer Radical Polymerization (BioATRP).
  • Formed ATP-coacervates and explored enzymatic control using alkaline phosphatase, Creatine phosphokinase, hexokinase, esterase, and urease.
  • Developed ERN-polymerization-induced transient coacervation (ERN-PIC) for system control.

Main Results:

  • Demonstrated adjustable dynamics of ATP-fueled transient coacervation using antagonistic and orthogonal enzyme pairs.
  • Showcased ATP-fueled coacervates' potential as cellular microreactors capable of enzymatic catalysis.
  • Achieved complete control over polymerization, coacervation, and dissolution using ERN-PIC.
  • Observed that the coacervation process influences functional properties like selective cargo uptake.

Conclusions:

  • The developed ERN strategy offers cutting-edge biomimetic applications and insights into cellular compartmentalization.
  • This approach bridges the gap between synthetic and biological systems.
  • Temporally programmed coacervation provides a promising platform for spatial arrangement of multienzyme cascades and designing artificial cells.