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Related Concept Videos

Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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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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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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Polymer Classification: Architecture01:14

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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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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.
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The extent of the...
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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Polymerization-Induced Helicity Inversion Driven by Stacking Modes and Self-Assembly Pathway Differentiation.

Xiaoxiao Cheng1, Tengfei Miao1, Haotian Ma1

  • 1State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.

Small (Weinheim an Der Bergstrasse, Germany)
|October 13, 2021
PubMed
Summary

Researchers developed a novel polymerization-induced helicity inversion strategy for azobenzene polymers. This method enables self-assembly and dynamic stereomutation without external stimuli, offering new insights into helical nanostructures.

Keywords:
azobenzenechiralityhelical nanofibersliquid crystallinepolymerization-induced helicity inversion

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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Area of Science:

  • Polymer Chemistry
  • Supramolecular Chemistry
  • Chirality Studies

Background:

  • Controlling hierarchical chirality in polymers is challenging, often requiring external stimuli.
  • Understanding the origin of chirality is crucial for nature and materials science.

Purpose of the Study:

  • To report the first self-assembly strategy for polymerization-induced helicity inversion (PIHI).
  • To achieve controlled packing and dynamic stereomutation of azobenzene building blocks during polymerization.
  • To investigate the mechanisms of helicity inversion and helix-helix transitions in polymeric nanofibers.

Main Methods:

  • In situ polymerization to induce self-assembly and helicity changes.
  • Analysis of azobenzene (Azo) building block packing and stereomutation.
  • Investigation of aggregation states (π-π stacking, H-, and J-aggregation).
  • Study of thermodynamic and kinetic control in helicity inversion.

Main Results:

  • Demonstrated PIHI without external stimuli.
  • Observed multiple helicity inversions and helix-helix transitions in nanofibers.
  • Confirmed mediation by transitions between π-π stacking, H-, and J-aggregation.
  • Revealed pathway-dependent interconversion processes in helicity inversion.

Conclusions:

  • PIHI offers a novel self-assembly strategy for chiral polymer systems.
  • Helicity inversion is driven by a dynamic interplay of aggregation states and kinetic/thermodynamic control.
  • Provides new insights into the origin and handedness control of helical nanostructures.