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Title: Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity

Abstract

Single molecule spectroscopy studies of local acidity along bifunctional acid-base gradients are reported. Gradients are prepared by directional vapor phase diffusion and subsequent reaction of 3-aminopropyl-trimethoxysilane with a uniform silica film. Gradient formation is confirmed by spectroscopic ellipsometry and by static water contact angle measurements. X-ray photoelectron spectroscopy is used to characterize the nitrogen content and degree of nitrogen protonation along the gradient. Nile Red is employed as the probe dye in single molecule spectroscopy studies of these gradients. While Nile Red is well-known for its solvent sensitivity, it is used here, for the first time, to sense the acid/base properties of the film in two-color wide-field fluorescence imaging experiments. The data reveal broad bimodal distributions of Nile Red emission spectra that vary along the gradient direction. The single-molecule results are consistent with solution-phase ensemble acid/base studies of the dye. The former reveal a gradual transition from a surface dominated by basic aminosilane sites at the high-amine end of the gradient to one dominated by acidic silanol sites at the low-amine end. The sub-diffraction-limited spatial resolution afforded by superlocalization of the single molecules reveals spatial correlations in the acid/base properties of the gradient over ~ 200 nm distances. Furthermore, thesemore » studies provide data relevant to the use of aminosilane-modified silica in bifunctional, cooperative chemical catalysis.« less

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Kansas State Univ., Manhattan, KS (United States)
  2. Virginia Commonwealth Univ., Richmond, VA (United States)
  3. Kansas State Univ., Manhattan, KS (United States); Miami Univ., Oxford, OH (United States)
Publication Date:
Research Org.:
Kansas State Univ., Manhattan, KS (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1874682
Grant/Contract Number:  
SC0002362
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 37; Journal Issue: 41; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Fluorescence; Molecules; Reaction mechanisms; Silica; X-ray photoelectron spectroscopy

Citation Formats

Usman, Abdulhafiz, Weatherbee, Shelby L., Collinson, Maryanne M., Hohn, Keith L., and Higgins, Daniel A. Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity. United States: N. p., 2021. Web. doi:10.1021/acs.langmuir.1c02059.
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Usman, Abdulhafiz, Weatherbee, Shelby L., Collinson, Maryanne M., Hohn, Keith L., & Higgins, Daniel A. Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity. United States. https://doi.org/10.1021/acs.langmuir.1c02059
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Usman, Abdulhafiz, Weatherbee, Shelby L., Collinson, Maryanne M., Hohn, Keith L., and Higgins, Daniel A. Mon . "Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity". United States. https://doi.org/10.1021/acs.langmuir.1c02059. https://www.osti.gov/servlets/purl/1874682.
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@article{osti_1874682,
title = {Single Molecule Spectroscopy Studies of Acid–Base Chemical Gradients Using Nile Red as a Probe of Local Surface Acidity},
author = {Usman, Abdulhafiz and Weatherbee, Shelby L. and Collinson, Maryanne M. and Hohn, Keith L. and Higgins, Daniel A.},
abstractNote = {Single molecule spectroscopy studies of local acidity along bifunctional acid-base gradients are reported. Gradients are prepared by directional vapor phase diffusion and subsequent reaction of 3-aminopropyl-trimethoxysilane with a uniform silica film. Gradient formation is confirmed by spectroscopic ellipsometry and by static water contact angle measurements. X-ray photoelectron spectroscopy is used to characterize the nitrogen content and degree of nitrogen protonation along the gradient. Nile Red is employed as the probe dye in single molecule spectroscopy studies of these gradients. While Nile Red is well-known for its solvent sensitivity, it is used here, for the first time, to sense the acid/base properties of the film in two-color wide-field fluorescence imaging experiments. The data reveal broad bimodal distributions of Nile Red emission spectra that vary along the gradient direction. The single-molecule results are consistent with solution-phase ensemble acid/base studies of the dye. The former reveal a gradual transition from a surface dominated by basic aminosilane sites at the high-amine end of the gradient to one dominated by acidic silanol sites at the low-amine end. The sub-diffraction-limited spatial resolution afforded by superlocalization of the single molecules reveals spatial correlations in the acid/base properties of the gradient over ~ 200 nm distances. Furthermore, these studies provide data relevant to the use of aminosilane-modified silica in bifunctional, cooperative chemical catalysis.},
doi = {10.1021/acs.langmuir.1c02059},
journal = {Langmuir},
number = 41,
volume = 37,
place = {United States},
year = {Mon Oct 04 00:00:00 EDT 2021},
month = {Mon Oct 04 00:00:00 EDT 2021}
}
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https://doi.org/10.1021/acs.langmuir.1c02059
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