Related Experiment Video
Updated: Jun 9, 2026
16:24
Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
Published on: August 2, 2012
Fluids density functional theory studies of supramolecular polymers at a hard surface
E S McGarrity1, J M Thijssen, N A M Besseling
1Engineering Thermodynamics Section, Process and Energy, Delft University of Technology, 2628 CA Delft, The Netherlands. e.s.mcgarrity@tudelft.nl
The Journal of Chemical Physics
|September 7, 2010
Summary
We developed a theory for reversible supramolecular polymers near surfaces. Polymer depletion length shows nonmonotonic behavior with concentration and can be controlled using end stoppers.
Area of Science:
- Physical Chemistry
- Soft Matter Physics
- Materials Science
Background:
- Supramolecular polymers are complex systems with unique properties.
- Understanding their behavior near surfaces is crucial for applications.
- Existing theories may not fully capture reversible polymer dynamics.
Purpose of the Study:
- To develop and apply a theoretical framework for reversible supramolecular polymers near hard surfaces.
- To investigate the influence of bonding scheme, concentration, and association energy on polymer properties.
- To analyze the impact of end-capping agents on polymer behavior.
Main Methods:
- Utilized a fluids density functional theory (DFT) adapted from Yu and Wu.
- Integrated DFT with Wertheim's first-order thermodynamic perturbation theory.
- Modeled supramolecular polymers as hard spheres with two associating sites.
Main Results:
- The model accurately reproduces behavior in dilute and overlap regimes.
- A nonmonotonic relationship was observed between polymer depletion length and concentration.
- The depletion length can be effectively tuned by adjusting the concentration of end-stopper monomers.
Conclusions:
- The developed DFT approach provides a robust tool for studying supramolecular polymers near surfaces.
- Control over polymer chain size and depletion is achievable through monomer concentration and end-capping.
- Findings are relevant for designing colloidal dispersions and understanding polymer-surface interactions.
Related Concept Videos
01:08Molecular 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...
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...
02:28Intermolecular Forces in Solutions
The formation of a solution is an example of a spontaneous process, a process that occurs under specified conditions without energy from some external source.
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called an ideal solution. A mixture of ideal gases (or gases such as helium and argon,...
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called an ideal solution. A mixture of ideal gases (or gases such as helium and argon,...
01:27Determination of Molar Masses of Polymers II
Polymer samples typically consist of macromolecular chains with a distribution of lengths, resulting in a range of molar masses rather than a single discrete value. Conventional descriptors such as the number-average molar mass and weight-average molar mass quantify this distribution but do not fully capture polymer behavior in solution..The viscosity-average molar mass provides a more realistic description of polymer behavior in solution because it accounts for the enhanced contribution of...
01:10Polymers: Molecular Weight Distribution
For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
01:22Surface Tension of Fluid
Surface tension is a fundamental property of fluids, occurring at the boundary between a liquid and a gas or between two immiscible liquids. This phenomenon arises from the cohesive forces between molecules at the fluid's surface, creating an effect similar to a stretched elastic membrane. Inside each fluid, molecules are equally attracted in all directions by neighboring molecules, but surface molecules experience a net inward force, resulting in surface tension.
Surface tension varies with...
Surface tension varies with...
01:24Van der Waals Interactions
Atoms and molecules interact with each other through intermolecular forces. These electrostatic forces arise from attractive or repulsive interactions between particles with permanent, partial, or temporary charges. The intermolecular forces between neutral atoms and molecules are ion–dipole, dipole–dipole, and dispersion forces, collectively known as van der Waals forces.Polar molecules have a partial positive charge on one end and a partial negative charge on the other end of the molecule,...