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Charge symmetry breaking in neutral polyzwitterions
Yeseul Lee1, Murugappan Muthukumar2
1Department of Polymer Science and Engineering, University of Massachusetts, Amherst, MA, USA.
Charge-neutral polyzwitterions exhibit rectified movement in electric fields due to differential counterion binding. This behavior arises from charge symmetry breaking, offering new insights into dipolar polymer dynamics.
Area of Science:
- Polymer physics
- Electrokinetic phenomena
- Solution chemistry
Background:
- The electrophoretic behavior of ionized groups in macromolecules is well-understood.
- The response of neutral or polar monomers in macromolecules to electric fields in aqueous solutions is largely unstudied.
- It remains unclear if neutral monomers offer only frictional resistance or actively contribute to electrophoretic mobility.
Purpose of the Study:
- To investigate the electrophoretic mobility of neutral polyzwitterions in aqueous solutions.
- To explore the influence of monomer dipole orientation and salt identity on polymer movement.
- To elucidate the mechanisms behind the response of charge-neutral polymers to electric fields.
Main Methods:
- Single-molecule electrophoresis experiments were conducted.
- Theoretical modeling was employed to analyze the experimental data.
- The study focused on polyzwitterions with charge-neutral repeat units containing acidic and positive charges.
Main Results:
- Charge-neutral polyzwitterions demonstrated rectified mobility, moving preferentially in one direction.
- Charge symmetry breaking was identified as the cause of rectified motion.
- Differential counterion binding, influenced by local dielectric constant gradients, was found to be responsible for charge symmetry breaking.
Conclusions:
- Neutral polyzwitterions can exhibit directed movement in electric fields, contrary to simple frictional resistance.
- The findings reveal a novel mechanism for controlling polymer motion via intrinsic charge distribution and counterion interactions.
- This research opens new avenues for understanding and utilizing dipolar polymers in various applications.
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