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Related Concept Videos

Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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 generated carbocation,...
Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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...
Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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 the...
Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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...
Polymers02:34

Polymers

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 properties that they exhibit. Additionally,...

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
16:24

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

Published on: August 2, 2012

Pathway complexity in supramolecular polymerization.

Peter A Korevaar1, Subi J George, Albert J Markvoort

  • 1Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands.

Nature
|January 20, 2012
PubMed
Summary
This summary is machine-generated.

Researchers observed supramolecular polymer formation, revealing two competing assembly pathways. By using a chiral auxiliary, they directed the self-assembly towards a specific, kinetically favored structure, demonstrating control over molecular organization.

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Area of Science:

  • Supramolecular chemistry
  • Materials science
  • Organic electronics

Background:

  • Self-assembly of organic molecules is crucial for functional materials.
  • Understanding molecular organization pathways is key to controlling material properties.
  • Existing models for protein fibril formation are complex and extend beyond simple nucleation.

Purpose of the Study:

  • To investigate the kinetic pathways of supramolecular polymer formation from π-conjugated oligomers.
  • To gain quantitative insights into the self-assembly process.
  • To demonstrate control over the final assembly structure using external stimuli.

Main Methods:

  • Time-resolved kinetic experiments to observe assembly formation.
  • Kinetic model calculations to analyze competing pathways.
  • Chiral auxiliary-directed self-assembly using tartaric acid.

Main Results:

  • Identified a kinetically favored metastable assembly that forms rapidly.
  • Revealed two parallel, competing self-assembly pathways with opposite helicity.
  • Demonstrated that a chiral auxiliary can selectively favor the kinetically controlled pathway.

Conclusions:

  • The self-assembly of π-conjugated oligomers involves complex kinetic pathways.
  • Chiral auxiliaries can be used to precisely control the thermodynamic outcome of self-assembly.
  • This provides a method to obtain metastable supramolecular assemblies on demand.