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Polymers

Polymers

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 properties that they exhibit. Additionally,...

Step-Growth Polymerization: Overview

Step-Growth Polymerization: Overview

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...

Molecular Weight of Step-Growth Polymers

Molecular Weight of Step-Growth Polymers

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.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...

Anionic Chain-Growth Polymerization: Mechanism

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.

Cationic Chain-Growth Polymerization: Mechanism

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,...

Radical Chain-Growth Polymerization: Chain Branching

Radical Chain-Growth Polymerization: Chain Branching

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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Related Experiment Video

Updated: Jun 4, 2026

DNA Nanotubes as a Versatile Tool to Study Semiflexible Polymers

DNA Nanotubes as a Versatile Tool to Study Semiflexible Polymers

Published on: October 25, 2017

End-monomer Dynamics in Semiflexible Polymers.

Michael Hinczewski¹, Xaver Schlagberger, Michael Rubinstein

¹Feza Gürsey Research Institute, TÜBITAK - Bosphorus University, Çengelköy 34684, Istanbul, Turkey.

|March 2, 2011

Summary

We investigated semiflexible polymer end-monomer dynamics, finding a new intermediate regime. This regime shows a drop in the mean squared displacement exponent below the conventional Zimm scaling due to hydrodynamic effects.

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Area of Science:

Polymer Physics
Soft Matter Physics
Computational Biophysics

Background:

Conflicting experimental results exist regarding the end-monomer dynamics of semiflexible polymers, specifically double-stranded DNA.
Previous studies reported either Rouse-like scaling (t^1/2) or Zimm scaling (t^2/3) for the mean squared displacement (MSD) at intermediate timescales.
These discrepancies highlight a need for a deeper understanding of polymer dynamics in relation to chain length and persistence length.

Purpose of the Study:

To resolve the experimental controversy surrounding end-monomer dynamics in semiflexible polymers.
To investigate the influence of chain length and persistence length on polymer dynamics using theoretical and simulation approaches.
To identify and characterize novel dynamical regimes beyond the established Rouse and Zimm models.

Main Methods:

Brownian hydrodynamic simulations were employed to model polymer behavior.
Dynamic mean-field theory and analytical scaling theories were utilized for theoretical analysis.
The effective local exponent of the end-monomer MSD was calculated to characterize dynamics.

Main Results:

A novel intermediate dynamical regime was discovered for semiflexible polymers.
In this regime, the effective exponent of the end-monomer MSD drops below the Zimm value (2/3) for longer chains, but does not reach the Rouse limit (1/2).
Hydrodynamic effects, particularly the crossover between short and long length scales, explain the observed anomalous dynamics.

Conclusions:

The study reconciles conflicting experimental findings by identifying a new dynamical regime.
Hydrodynamic interactions play a crucial role in governing the end-monomer dynamics of semiflexible polymers.
The findings provide a more comprehensive theoretical framework for understanding polymer diffusion.