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Cationic Chain-Growth Polymerization: Mechanism00:57

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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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Polymer Classification: Crystallinity01:21

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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
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Intrinsically disordered proteins are a group of proteins that do not fold into specific three-dimensional structures. Their structural flexibility allows them to complement ordered proteins to perform functions that are inaccessible to rigid structures. They are more common in eukaryotes than prokaryotes and may either be exclusively intrinsically disordered or hybrid proteins, consisting of a mix of ordered and disordered regions. The absence of a rigid structure in these proteins can be...
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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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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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Molecular Weight of Step-Growth Polymers01:08

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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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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Sequence disorder-induced first order phase transition in confined polyelectrolytes.

V Stepanyan1, A Badasyan2, V Morozov3

  • 1Yerevan State University, Yerevan, Armenia.

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Disorder in flexible polyelectrolyte chains causes enhanced localization and a phase transition, altering pressure between surfaces and preventing bridging attraction.

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Area of Science:

  • Statistical mechanics
  • Polymer physics
  • Physical chemistry

Background:

  • Polyelectrolytes are polymers with charged monomers, exhibiting complex behavior due to electrostatic interactions.
  • Understanding polyelectrolyte behavior is crucial in fields ranging from biology to materials science.
  • Disorder in polymer sequences can significantly influence macroscopic properties.

Purpose of the Study:

  • To investigate the statistical mechanical model of a flexible polyelectrolyte with quenched disorder.
  • To analyze the free energy and monomer density profile in a confined system without electrolyte screening.
  • To determine the impact of contour sequence disorder on polyelectrolyte localization and phase transitions.

Main Methods:

  • Development of a statistical mechanical model for a flexible polyelectrolyte.
  • Inclusion of long-range electrostatic interactions and short-range disorder fields.
  • Calculation of free energy and monomer density for a system confined between two charged surfaces.

Main Results:

  • Contour sequence disorder enhances polyelectrolyte chain localization.
  • A first-order phase transition occurs at a critical inter-surface spacing.
  • The phase transition causes an abrupt pressure change from negative to positive values.

Conclusions:

  • Quenched disorder drives significant changes in polyelectrolyte behavior within confined geometries.
  • The observed phase transition alters inter-surface forces, suppressing bridging attraction.
  • This study provides insights into the role of disorder in polyelectrolyte systems.