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Title: Tailoring Surface Properties through in Situ Functionality Gradients in Reactively Modified Poly(2-vinyl-4,4-dimethyl azlactone) Thin Films

Abstract

Generating physical or chemical gradients in thin-film scaffolds is an efficient approach for screening and optimizing an interfacial structure or chemical functionality to create tailored surfaces that are useful because of their wetting, antifouling, or barrier properties. In this paper, the relationship between the structure of poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes created by the preferential assembly of poly(glycidyl methacrylate)-block-PVDMA diblock copolymers and the ability to chemically modify the PVDMA chains in situ to create a gradient in functionality are examined to investigate how the extent of functionalization affects the interfacial and surface properties. The introduction of a chemical gradient by controlled immersion allows reactive modification to generate position-dependent properties that are assessed by ellipsometry, attenuated total reflectance-Fourier transform infrared spectroscopy, contact angle measurements, and atomic force microscopy imaging. After functionalization of the azlactone rings with n-alkyl amines, ellipsometry confirms an increase in thickness and contact angle measurements support an increase in hydrophobicity along the substrate. These results are used to establish relationships between layer thickness, reaction time, position, and the extent of functionalization and demonstrate that gradual immersion into the functionalizing solution results in a linear change in chemical functionality along the surface. Finally, these findings broadly support efforts to producemore » tailored surfaces by in situ chemical modification, having application as tailored membranes, protein resistant surfaces, or sensors.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1468219
Grant/Contract Number:  
[AC05-00OR22725; 1133320; 1512221]
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
[ Journal Volume: 34; Journal Issue: 18]; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Aden, Bethany, Street, Dayton P., Hopkins, Benjamin W., Lokitz, Bradley S., and Kilbey, S. Michael. Tailoring Surface Properties through in Situ Functionality Gradients in Reactively Modified Poly(2-vinyl-4,4-dimethyl azlactone) Thin Films. United States: N. p., 2018. Web. doi:10.1021/acs.langmuir.8b00195.
Aden, Bethany, Street, Dayton P., Hopkins, Benjamin W., Lokitz, Bradley S., & Kilbey, S. Michael. Tailoring Surface Properties through in Situ Functionality Gradients in Reactively Modified Poly(2-vinyl-4,4-dimethyl azlactone) Thin Films. United States. doi:10.1021/acs.langmuir.8b00195.
Aden, Bethany, Street, Dayton P., Hopkins, Benjamin W., Lokitz, Bradley S., and Kilbey, S. Michael. Wed . "Tailoring Surface Properties through in Situ Functionality Gradients in Reactively Modified Poly(2-vinyl-4,4-dimethyl azlactone) Thin Films". United States. doi:10.1021/acs.langmuir.8b00195. https://www.osti.gov/servlets/purl/1468219.
@article{osti_1468219,
title = {Tailoring Surface Properties through in Situ Functionality Gradients in Reactively Modified Poly(2-vinyl-4,4-dimethyl azlactone) Thin Films},
author = {Aden, Bethany and Street, Dayton P. and Hopkins, Benjamin W. and Lokitz, Bradley S. and Kilbey, S. Michael},
abstractNote = {Generating physical or chemical gradients in thin-film scaffolds is an efficient approach for screening and optimizing an interfacial structure or chemical functionality to create tailored surfaces that are useful because of their wetting, antifouling, or barrier properties. In this paper, the relationship between the structure of poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes created by the preferential assembly of poly(glycidyl methacrylate)-block-PVDMA diblock copolymers and the ability to chemically modify the PVDMA chains in situ to create a gradient in functionality are examined to investigate how the extent of functionalization affects the interfacial and surface properties. The introduction of a chemical gradient by controlled immersion allows reactive modification to generate position-dependent properties that are assessed by ellipsometry, attenuated total reflectance-Fourier transform infrared spectroscopy, contact angle measurements, and atomic force microscopy imaging. After functionalization of the azlactone rings with n-alkyl amines, ellipsometry confirms an increase in thickness and contact angle measurements support an increase in hydrophobicity along the substrate. These results are used to establish relationships between layer thickness, reaction time, position, and the extent of functionalization and demonstrate that gradual immersion into the functionalizing solution results in a linear change in chemical functionality along the surface. Finally, these findings broadly support efforts to produce tailored surfaces by in situ chemical modification, having application as tailored membranes, protein resistant surfaces, or sensors.},
doi = {10.1021/acs.langmuir.8b00195},
journal = {Langmuir},
number = [18],
volume = [34],
place = {United States},
year = {2018},
month = {4}
}

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