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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

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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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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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Anionic Chain-Growth Polymerization: Overview01:20

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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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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.
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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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Kinetics of Polyampholyte Dimerization: Influence of Charge Sequences.

Seowon Kim1, Nam-Kyung Lee1, Youngkyun Jung2

  • 1Department of Physics and Astronomy, Sejong University, Seoul 05006, Republic of Korea.

Polymers
|October 26, 2024
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Summary

Polyampholytes

Keywords:
IDPdimerizationpolyampholytespolyelectrolytes

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Area of Science:

  • Biochemistry
  • Polymer Science
  • Computational Chemistry

Background:

  • Polyampholytes (PAs) display complex behaviors influenced by their charge distribution.
  • Intrinsically disordered proteins (IDPs) are crucial for cellular functions due to their dynamic nature and ability to form transient complexes.
  • The sequence of charged residues significantly impacts the properties of IDPs.

Purpose of the Study:

  • To investigate the kinetics of polyampholyte dimerization.
  • To elucidate the mechanisms governing dimer formation and dissociation rates.
  • To understand how charge sequence influences the structural and dynamical properties of polyampholytic IDPs.

Main Methods:

  • Molecular dynamics simulations were employed to study polyampholytes with non-zero net charges.
  • Theoretical analyses were conducted to examine the influence of charge sequences on dimerization kinetics.
  • The study focused on parameters like charge blockiness and tail composition.

Main Results:

  • Charge sequence, particularly the blockiness of the minority charge group and tail composition, significantly affects dimerization kinetics.
  • Increased blockiness and a higher proportion of majority charges in tails slow dimer dissociation.
  • Extended central blocks of the majority charge promote structural diversity within dimer states.

Conclusions:

  • Sequence-specific effects are critical for the aggregation and dissociation of polyampholytes and polyampholytic IDPs.
  • Dimer states exhibit longer durations than typical block inter-contacts, especially when multiple blocks are involved.
  • Understanding these principles is key to predicting the behavior of IDPs in cellular environments.