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Three-Dimensional pH Mapping within Model Hybrid Xerogel Thin Films.

Joel F Destino¹, Andrew K Craft¹, Frank V Bright¹

¹Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York , Buffalo, New York 14260-3000, United States.

Langmuir : the ACS Journal of Surfaces and Colloids

|April 9, 2017

Summary

Hybrid xerogel films on Al2O3 show distinct acidic or basic domains important for marine antifouling. These chemically segregated regions, visualized with confocal microscopy, offer unique properties for surface coatings.

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Area of Science:

Materials Science
Surface Chemistry
Nanotechnology

Background:

Hybrid xerogel films composed of carboxyethylsilanetriol (COE) and tetraethoxysilane (TEOS), or 3-aminopropyltriethoxysilane (APTES), n-octyltriethoxysilane (C8), and TEOS are formed on Al2O3 substrates.
These films exhibit chemically segregated domains with unique chemistries and topographies, which are crucial for marine antifouling applications.

Purpose of the Study:

To determine the three-dimensional pH distribution within hybrid xerogel films.
To investigate the relationship between chemical composition, topography, and pH in these films.
To understand the structural and chemical characteristics relevant to marine antifouling.

Main Methods:

Utilized a ratiometric fluorescent probe, 5 (and 6)-carboxy SNARF-1 (C.SNARF-1), for pH determination.

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Employed confocal fluorescence microscopy to visualize and analyze pH in three dimensions within the hybrid films.

Analyzed film topography and chemical segregation at different interfaces (solution-film and film-Al2O3).

Main Results:

COE/TEOS films displayed acidic (pH < 7) dendritic features (4-5 μm diameter) that decreased in size towards the Al2O3 interface.
APTES/C8/TEOS films showed basic (pH > 7) columnar mesa features (1-3 μm diameter) extending through the film.
Significant variations in pH and chemical composition (COE or APTES mole fraction) were observed across different film depths and domains.

Conclusions:

The study successfully mapped the 3D pH landscape of hybrid xerogel films, revealing distinct acidic and basic domains.
The findings highlight the structure-property relationships in these films, with potential for tailored marine antifouling coatings.
Confocal fluorescence microscopy with C.SNARF-1 is an effective method for characterizing pH heterogeneity in complex hybrid materials.