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Related Concept Videos

Polymers02:34

Polymers

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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...
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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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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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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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Confocal Imaging of Confined Quiescent and Flowing Colloid-polymer Mixtures
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Polymer escape from a confining potential.

Harri Mökkönen1, Timo Ikonen1, Hannes Jónsson1

  • 1Department of Applied Physics and COMP CoE, Aalto University School of Science, P.O. Box 11100, FIN-00076 Aalto, Espoo, Finland.

The Journal of Chemical Physics
|February 12, 2014
PubMed
Summary
This summary is machine-generated.

Polymer escape rates from confining potentials differ for self-avoiding and ideal chains. Longer self-avoiding polymers escape faster due to crowding, while ideal chains show a monotonic decrease in escape rate with length.

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Area of Science:

  • Polymer physics
  • Statistical mechanics
  • Computational chemistry

Background:

  • Understanding polymer dynamics in confined environments is crucial for various applications.
  • Previous studies often simplified polymer behavior or used shorter chain lengths.

Purpose of the Study:

  • To investigate the escape rates of polymers from a 2D potential well.
  • To analyze the influence of polymer length and chain architecture (self-avoiding vs. ideal) on escape dynamics.

Main Methods:

  • Simulated long timescale Langevin trajectories using path integral hyperdynamics.
  • Employed self-avoiding and ideal chain models up to 80 beads.
  • Utilized thermodynamic averaging and Kramers rate theory for effective potential analysis.

Main Results:

  • Self-avoiding polymers exhibit a minimum escape rate at intermediate lengths, with rates increasing for longer chains due to crowding.
  • Ideal polymers show a monotonic decrease in escape rate with increasing length.
  • Kramers rate theory with centroid variable overestimates escape rates, especially for longer polymers.

Conclusions:

  • The escape mechanism is influenced by polymer length and chain conformation.
  • A simple centroid-based transition state is insufficient for accurately predicting polymer escape rates.
  • Accurate transition state definitions require considering both polymer shape and location.