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Title: Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization

Abstract

The pH at silica-water interfaces (pH int) was measured by grafting a dual emission fluorescent probe (SNARF) onto the surface of mesoporous silica nanoparticles (MSN). The values of pH int of SNARF-MSN suspended in water were different from the pH of the bulk solution (pH bulk). The addition of acid or base to aqueous suspensions of SNARF-MSN induced much larger changes in pH bulk than pH int, indicating that the interface has buffering capacity. Grafting additional organic functional groups onto the surface of SNARF-MSN controls the pH int of its buffering region. The responses of pH int to variations in pH bulk are consistent with the acid/base properties of the surface groups as determined by their pK a and are affected by electrostatic interactions between charged interfacial species as evidenced by the dependence of ζ-potential on pH bulk. Finally, as a proof of principle, we demonstrate that the hydrolysis rate of an acid-sensitive acetal can be controlled by adjusting pH int 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), 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.
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Singappuli-Arachchige, Dilini, & Slowing, Igor I. Control of interfacial pH in mesoporous silica nanoparticles via surface functionalization. United States. doi:10.1063/1.5138912.
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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.
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@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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DOI:  10.1063/1.5138912
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