Atomically Resolved Characterization of Optically Driven Ligand Reconfiguration on Nanoparticle Catalyst Surfaces.
Mary O Olagunju1, Yang Liu2, Anatoly I Frenkel2,3
1Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, Florida 33146, United States.
ACS Applied Materials & Interfaces
|September 9, 2021
Summary
Researchers demonstrated remote control of peptide ligands on gold nanoparticles using photoswitches. This surface ligand reconfiguration impacts catalytic activity, opening doors for applications in drug delivery and sensing.
Area of Science:
- Nanomaterials Science
- Surface Chemistry
- Catalysis
Background:
- Dynamic ligand layers on nanoparticle surfaces are crucial for enhancing material functionality.
- Peptide-based ligands with incorporated photoswitches can undergo remote structural changes when adsorbed onto nanoparticle surfaces.
- Remote actuation of surface ligands offers potential for multifunctionality and advanced material control.
Purpose of the Study:
- To provide direct spectroscopic evidence of remote actuation for photoswitchable peptides on gold nanoparticles.
- To correlate changes in surface ligand conformation with catalytic activity.
- To explore the influence of substrate structure on the catalytic performance of these functionalized nanoparticles.
Main Methods:
- Utilizing X-ray absorption fine structure (XAFS) spectroscopy to analyze changes in gold-ligand coordination (Au-X, where X = C or N) before and after photoswitching.
- Investigating the catalytic reduction of nitrophenol using the functionalized gold nanoparticles.
- Varying the structure of the nitrophenol substrate to assess its impact on catalytic reactivity.
Main Results:
- Direct spectroscopic evidence confirmed the remote actuation of photoswitchable peptides on gold nanoparticle surfaces.
- Changes in Au-X coordination numbers indicated alterations in surface ligand conformation post-photoswitching.
- Catalytic activity for nitrophenol reduction was directly correlated with these conformational changes and sensitive to substrate structure.
Conclusions:
- Surface ligands on nanoparticles can be remotely reconfigured, offering a powerful tool for material control.
- This remote reconfiguration capability has significant implications for catalysis, drug delivery, and sensing applications.
- The interplay between ligand conformation and substrate structure dictates catalytic reactivity, enabling tunable material performance.


