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Perfluorocarbon nanodroplets (PFCnDs) are ultrasound contrast agents that phase-transition from liquid nanodroplets to gas microbubbles when activated by laser irradiation or insonated with an ultrasound pulse. The dynamics of PFCnDs can vary drastically depending on the nanodroplet composition, including the lipid shell properties. In this paper, we investigate the effect of varying the ratio of PEGylated to non-PEGylated phospholipids in the outer shell of PFCnDs on the acoustic nanodroplet vaporization (liquid to gas phase transition) and inertial cavitation (rapid collapse of the vaporized nanodroplets) dynamics in vitro when insonated with focused ultrasound. Nanodroplets with a high concentration of PEGylated lipids had larger diameters and exhibited greater variance in size distribution compared to nanodroplets with lower proportions of PEGylated lipids in the lipid shell. PFCnDs with a lipid shell composed of 50:50 PEGylated to non-PEGylated lipids yielded the highest B-mode image intensity and duration, as well as the greatest pressure difference between acoustic droplet vaporization onset and inertial cavitation onset. We demonstrate that slight changes in lipid shell composition of PFCnDs can significantly impact droplet phase transitioning and inertial cavitation dynamics. These findings can help guide researchers to fabricate PFCnDs with optimized compositions for their specific applications.
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Electrochemical quantification of accelerated FADGDH rates in aqueous nanodroplets
Enzymes are molecules that catalyze reactions critical to life. These catalysts are often studied in bulk water, where the influence of water volume on reactivity is neglected. Here, we demonstrate rate enhancement of up to two orders of magnitude for enzymes trapped in submicrometer water nanodroplets suspended in 1,2-dichloroethane. When single nanodroplets irreversibly adsorb onto an ultramicroelectrode surface, enzymatic activity is apparent in the amperometric current-time trace if the ultramicroelectrode generates the enzyme cofactor. Nanodroplet volume is easily accessible by integrating the current-time response and using Faraday’s Law. The single nanodroplet technique allows us to plot the enzyme’s activity as a function of nanodroplet size, revealing a strong inverse relationship. Finite element simulations confirm our experimental results and offer insights into parameters influencing single nanodroplet enzymology. These results provide a framework to profoundly influence the understanding of chemical reactivity at the nanoscale.
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- Award ID(s):
- 2003587
- PAR ID:
- 10249818
- Publisher / Repository:
- Proceedings of the National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 118
- Issue:
- 25
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- Article No. e2025726118
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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