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Related Experiment Video

Updated: May 27, 2025

Study of Short Peptide Adsorption on Solution Dispersed Inorganic Nanoparticles Using Depletion Method

Study of Short Peptide Adsorption on Solution Dispersed Inorganic Nanoparticles Using Depletion Method

Published on: April 11, 2020

Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption.

Pan Sun¹, Nabarupa Bhattacharjee¹, Jeffrey D Einkauf¹

¹Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States.

The Journal of Physical Chemistry Letters

|February 20, 2025

Summary

This summary is machine-generated.

This study reveals that hydrophobic tails slow ligand adsorption to interfaces by forming bulk colloids. This kinetic effect offers new strategies for selective chemical separations beyond traditional equilibrium models.

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Area of Science:

Chemical Engineering
Physical Chemistry
Materials Science

Background:

Complex chemical phenomena and transport are governed by competing bulk and interfacial processes.
Traditional approaches often frame these competitions thermodynamically, overlooking kinetic opportunities away from equilibrium.
Transient species and nonequilibrium dynamics offer pathways to unconventional reaction outcomes and separations.

Purpose of the Study:

To investigate competitive bulk and interfacial reaction pathways using ligands with tunable hydrophobicity.
To explore kinetic control over selective chemical separations by modifying molecular extractants.
To leverage nonequilibrium phenomena for novel separation strategies.

Main Methods:

Synthesis of iminoguanidinium-based ligands with varying alkyl tail complexity for selective sulfate (SO₄^2-) complexation.
Utilizing sum frequency generation (SFG) vibrational spectroscopy to monitor interfacial adsorption dynamics.
Characterizing the formation and behavior of bulk colloidal species.

Main Results:

Ligand adsorption to the air-aqueous interface significantly slowed with increasing alkyl tail hydrophobicity.
Formation of bulk colloidal species was identified as a kinetic bottleneck, inhibiting surface adsorption.
The propensity of colloids for sulfate complexation directly impacted the rate of interfacial transfer.

Conclusions:

Kinetic control, specifically through bulk colloidal formation, can dictate interfacial phenomena in chemical separations.
This nonequilibrium kinetic effect provides a mechanism for achieving unconventional selectivity, favoring interfacial transport of weakly coordinating species.
The findings challenge equilibrium-based descriptions and highlight the importance of interfacial dynamics in chemical separations.