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Related Concept Videos

Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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,...
Types of Step-Growth Polymers: Polyesters01:20

Types of Step-Growth Polymers: Polyesters

The introduction of polyesters has brought major development to the textile industry. The wrinkle-free behavior of polyester blends has eliminated the need for starching and ironing clothes.
Polyesters are commonly prepared from terephthalic acid and ethylene glycol; the crude product is known as poly(ethylene terephthalate) or PET. However, polyesters are synthesized industrially by transesterification of dimethyl terephthalate with ethylene glycol at 150 °C. The two reactants and the polymer...
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,...
Ion Exchange01:17

Ion Exchange

Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or basic...
Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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...
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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 acceptor.

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Fabricating Degradable Thermoresponsive Hydrogels on Multiple Length Scales via Reactive Extrusion, Microfluidics, Self-assembly, and Electrospinning
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Degradable Cationic Polyesters with Tunable Anion-Induced Upper Critical Solution Temperature Coacervation.

Maria Kaliva1,2, Maria Karouzou1,2, Maria Vamvakaki1,2

  • 1Department of Materials Science and Engineering, University of Crete, Heraklion, Crete 700 13, Greece.

Biomacromolecules
|June 30, 2026
PubMed
Summary

Researchers developed degradable cationic polyesters with tunable upper critical solution temperature (UCST) phase behavior triggered by anions. These polymers exhibit pH responsiveness and reversible self-coacervation for potential applications in drug delivery.

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Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by π-π Stacking Interactions
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Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by π-π Stacking Interactions

Published on: October 10, 2016

Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Biomaterials

Background:

  • Developing smart polymers with tunable phase transitions is crucial for advanced applications.
  • Stimuli-responsive materials that exhibit controlled phase separation are of significant interest.
  • Understanding the interplay between polymer structure, counterions, and phase behavior is essential.

Purpose of the Study:

  • To design and synthesize degradable cationic polyesters with pH-responsive and anion-induced UCST phase behavior.
  • To investigate the influence of different anions (Cl-, BF4-, salicylate) on polymer phase transitions and coacervation.
  • To evaluate the hydrolytic degradation characteristics of these polyesters under physiological conditions.

Main Methods:

  • Synthesis of main-chain cationic polyesters with ionizable amine side groups.
  • Investigation of Upper Critical Solution Temperature (UCST) transitions using cloud point measurements.
  • Characterization of anion-induced phase separation and reversible self-coacervation.
  • Assessment of hydrolytic degradation rates under varying conditions.

Main Results:

  • Polymers exhibited tunable UCST phase behavior (8-91 °C) controlled by anion type, pH, concentration, and anion-to-cation ratio.
  • Anion-induced transitions were observed with NaCl, NaBF4, and salicylate.
  • Liquid-liquid phase separation into dynamic coacervate droplets was confirmed.
  • Hydrolytic degradation was counterion-dependent; PE-Cys-Cl degraded significantly, while PE-Cys-BF4 showed minimal degradation.

Conclusions:

  • Degradable cationic polyesters offer a versatile platform for anion-triggered UCST phase separation and reversible coacervation.
  • The materials demonstrate tunable properties and counterion-dependent degradation, suitable for responsive applications.
  • Potential applications include anion sensing and advanced drug delivery systems.