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Metal nanoparticles are attracting interest for their light-absorption properties, but such materials are known to dynamically evolve under the action of chemical and physical perturbations, resulting in changes in their structure and composition. Using a transmission electron microscope equipped for optical excitation of the specimen, the structural evolution of Cu-based nanoparticles under simultaneous electron beam irradiation and plasmonic excitation was investigated with high spatiotemporal resolution. These nanoparticles initially have a Cu core–Cu2O oxide shell structure, but over the course of imaging, they undergo hollowing via the nanoscale Kirkendall effect. We captured the nucleation of a void within the core, which then rapidly grows along specific crystallographic directions until the core is hollowed out. Hollowing is triggered by electron-beam irradiation; plasmonic excitation enhances the kinetics of the transformation likely by the effect of photothermal heating.
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Unraveling the Nano–Bio Interface Interactions of a Lipase Adsorbed on Gold Nanoparticles under Laser Excitation
The complex nature and structure of biomolecules and nanoparticles and their interactions make it challenging to achieve a deeper understanding of the dynamics at the nano–bio interface of enzymes and plasmonic nanoparticles subjected to light excitation. In this study, circular dichroism (CD) and Raman spectroscopic experiments and molecular dynamics (MD) simulations were used to investigate the potential changes at the nano–bio interface upon plasmonic excitation. Our data showed that photothermal and thermal heating induced distinct changes in the secondary structure of a model nanobioconjugate composed of lipase fromCandida antarcticafraction B (CALB) and gold nanoparticles (AuNPs). The use of a green laser led to a substantial decrease in the α-helix content of the lipase from 66% to 13% and an increase in the β-sheet content from 5% to 31% compared to the initial conformation of the nanobioconjugate. In contrast, the differences under similar thermal heating conditions were only 55% and 11%, respectively. This study revealed important differences related to the enzyme secondary structure, enzyme–nanoparticle interactions, and the stability of the enzyme catalytic triad (Ser105-Asp187-His224), influenced by the instantaneous local temperature increase generated from photothermal heating compared to the slower rate of thermal heating of the bulk. These results provide valuable insights into the interactions between biomolecules and plasmonic nanoparticles induced by photothermal heating, advancing plasmonic biocatalysis and related fields.
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- Award ID(s):
- 2019745
- PAR ID:
- 10512022
- Publisher / Repository:
- ACS Publications
- Date Published:
- Journal Name:
- Langmuir
- Volume:
- 40
- Issue:
- 11
- ISSN:
- 0743-7463
- Page Range / eLocation ID:
- 5663 to 5672
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.langmuir.3c02994
