Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization
Abstract
The pH at silica-water interfaces (pHint) was measured by grafting a dual emission fluorescent probe (SNARF) onto the surface of mesoporous silica nanoparticles (MSN). The values of pHint of SNARF-MSN suspended in water were different from the pH of the bulk solution (pHbulk). The addition of acid or base to aqueous suspensions of SNARF-MSN induced much larger changes in pHbulk than pHint, indicating that the interface has buffering capacity. Grafting additional organic functional groups onto the surface of SNARF-MSN controls the pHint of its buffering region. The responses of pHint to variations in pHbulk are consistent with the acid/base properties of the surface groups as determined by their pKa and are affected by electrostatic interactions between charged interfacial species as evidenced by the dependence of ζ-potential on pHbulk. Finally, as a proof of principle, we demonstrate that the hydrolysis rate of an acid-sensitive acetal can be controlled by adjusting pHint via suitable functionalization of the MSN surface. Our findings can lead to the development of nanoreactors that protect sensitive species from adverse conditions and tune their chemical reactivity.
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1594062
- Alternate Identifier(s):
- OSTI ID: 1591968
- Report Number(s):
- IS-J-10118
Journal ID: ISSN 0021-9606
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 152; Journal Issue: 3; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Singappuli-Arachchige, Dilini, and Slowing, Igor I. Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization. United States: N. p., 2020.
Web. doi:10.1063/1.5138912.
Singappuli-Arachchige, Dilini, & Slowing, Igor I. Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization. United States. doi:10.1063/1.5138912.
Singappuli-Arachchige, Dilini, and Slowing, Igor I. Thu .
"Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization". United States. doi:10.1063/1.5138912. https://www.osti.gov/servlets/purl/1594062.
@article{osti_1594062,
title = {Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization},
author = {Singappuli-Arachchige, Dilini and Slowing, Igor I.},
abstractNote = {The pH at silica-water interfaces (pHint) was measured by grafting a dual emission fluorescent probe (SNARF) onto the surface of mesoporous silica nanoparticles (MSN). The values of pHint of SNARF-MSN suspended in water were different from the pH of the bulk solution (pHbulk). The addition of acid or base to aqueous suspensions of SNARF-MSN induced much larger changes in pHbulk than pHint, indicating that the interface has buffering capacity. Grafting additional organic functional groups onto the surface of SNARF-MSN controls the pHint of its buffering region. The responses of pHint to variations in pHbulk are consistent with the acid/base properties of the surface groups as determined by their pKa and are affected by electrostatic interactions between charged interfacial species as evidenced by the dependence of ζ-potential on pHbulk. Finally, as a proof of principle, we demonstrate that the hydrolysis rate of an acid-sensitive acetal can be controlled by adjusting pHint via suitable functionalization of the MSN surface. Our findings can lead to the development of nanoreactors that protect sensitive species from adverse conditions and tune their chemical reactivity.},
doi = {10.1063/1.5138912},
journal = {Journal of Chemical Physics},
number = 3,
volume = 152,
place = {United States},
year = {2020},
month = {1}
}
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