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Related Concept Videos

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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Intermolecular Forces03:13

Intermolecular Forces

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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

2.2K
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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Aqueous Solutions and Heats of Hydration02:42

Aqueous Solutions and Heats of Hydration

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Water and other polar molecules are attracted to ions. The electrostatic attraction between an ion and a molecule with a dipole is called an ion-dipole attraction. These attractions play an important role in the dissolution of ionic compounds in water.
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Colloidal precipitates01:09

Colloidal precipitates

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The high insolubility of some precipitates can result in an unfavorable relative supersaturation. This can lead to colloidal particles with a large surface-to-mass ratio, where adsorption is promoted. For instance, in the precipitation of silver chloride, silver ions are adsorbed on the surface of the colloidal particles, forming a primary layer. This layer attracts ions of opposite charge (such as nitrate ions), forming a diffuse secondary layer of adsorbed ions. This electric double layer...
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Updated: Aug 30, 2025

Assembly and Characterization of Polyelectrolyte Complex Micelles
08:44

Assembly and Characterization of Polyelectrolyte Complex Micelles

Published on: March 2, 2020

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Driving force and pathway in polyelectrolyte complex coacervation.

Shensheng Chen1, Zhen-Gang Wang1

  • 1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125.

Proceedings of the National Academy of Sciences of the United States of America
|August 29, 2022
PubMed
Summary
This summary is machine-generated.

Polyelectrolyte complex coacervation is primarily driven by entropy, not energy. Accounting for electrostatic entropy from solvent reorganization reconciles simulations with experiments, revealing key insights into this phase separation process.

Keywords:
coarse-grained simulationentropypolarizationpolyelectrolyte complex coacervationthermodynamic driving force

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

  • Physical Chemistry
  • Polymer Science
  • Soft Matter Physics

Background:

  • Discrepancy exists between experimental and simulation findings on the thermodynamic driving force of polyelectrolyte complex coacervation.
  • Experiments suggest entropy dominates, while coarse-grained simulations often report significant energetic contributions.

Purpose of the Study:

  • To investigate the thermodynamic driving forces in polyelectrolyte complex coacervation using molecular dynamics simulations.
  • To reconcile the discrepancy between experimental and simulation results regarding the role of entropy and energy.

Main Methods:

  • Coarse-grained, implicit-solvent molecular dynamics simulations.
  • Thermodynamic analysis, including potential of mean force (PMF) calculations.
  • Analysis of electrostatic entropy contributions due to solvent reorganization.

Main Results:

  • The temperature dependence of water's dielectric constant introduces a substantial entropic contribution to electrostatic interactions.
  • When electrostatic entropy is considered, both complexation and condensation stages are entropy-driven, aligning with experimental observations.
  • Electrostatic entropy, not counterion release, is the main entropic driver for weak to intermediate electrostatic strengths.
  • The supernatant phase is mainly composed of polyion pairs, with a minor concentration of free polyelectrolytes.

Conclusions:

  • The study reconciles simulation and experimental data by incorporating electrostatic entropy.
  • Electrostatic entropy, driven by solvent reorganization, is crucial for understanding polyelectrolyte complex coacervation.
  • Polyion pair-pair attraction via induced polarization initiates the coacervation pathway.