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Title: Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions

Abstract

Functional soft interfaces are of interest for a variety of technologies. We describe three methods for preparing substrates with alkyne groups, which show versatility for 'click' chemistry reactions. Two of the methods have the same root: formation of thin, covalently attached, reactive interfacial layers of poly(glycidyl methacrylate) (PGMA) via spin coating onto silicon wafers followed by reactive modification with either propargylamine or 5-hexynoic acid. The amine or the carboxylic acid moieties react with the epoxy groups of PGMA, creating interfacial polymer layers decorated with alkyne groups. The third method consists of using copolymers comprising glycidyl methacrylate and propargyl methacrylate (pGP). The pGP copolymers are spin coated and covalently attached on silicon wafers. For each method, we investigate the factors that control film thickness and content of alkyne groups using ellipsometry, and study the nanophase structure of the films using neutron reflectometry. Azide-terminated polymers of methacrylic acid and 2-vinyl-4,4-dimethylazlactone synthesized via reversible addition-fragmentation chain transfer polymerization were attached to the alkyne-modified substrates using 'click' chemistry, and grafting densities in the range of 0.007-0.95 chains nm{sup -2} were attained. The maximum density of alkyne groups attained by functionalization of PGMA with propargylamine or 5-hexynoic acid was approximately 2 alkynes nm{sup -3}. Themore » alkyne content obtained by the three decorating approaches was sufficiently high that it was not the limiting factor for the click reaction of azide-capped polymers.« less

Authors:
 [1];  [2];  [3];  [1];  [2];  [2]
  1. University of Tennessee, Knoxville (UTK)
  2. ORNL
  3. Clemson University
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1014237
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 27; Journal Issue: 10; Journal ID: ISSN 0743-7463
Country of Publication:
United States
Language:
English
Subject:
functional interfaces; click chemistry; neutron reflectometry

Citation Formats

Soto-Cantu, Dr. Erick, Lokitz, Bradley S, Hinestrosa Salazar, Juan Pablo, Deodhar, Chaitra, Messman, Jamie M, Ankner, John Francis, and Kilbey, II, S Michael. Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions. United States: N. p., 2011. Web. doi:10.1021/la2000798.
Soto-Cantu, Dr. Erick, Lokitz, Bradley S, Hinestrosa Salazar, Juan Pablo, Deodhar, Chaitra, Messman, Jamie M, Ankner, John Francis, & Kilbey, II, S Michael. Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions. United States. https://doi.org/10.1021/la2000798
Soto-Cantu, Dr. Erick, Lokitz, Bradley S, Hinestrosa Salazar, Juan Pablo, Deodhar, Chaitra, Messman, Jamie M, Ankner, John Francis, and Kilbey, II, S Michael. Sat . "Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions". United States. https://doi.org/10.1021/la2000798.
@article{osti_1014237,
title = {Versatility of Alkyne-Modified Poly(Glycidyl Methacrylate) Layers for Click Reactions},
author = {Soto-Cantu, Dr. Erick and Lokitz, Bradley S and Hinestrosa Salazar, Juan Pablo and Deodhar, Chaitra and Messman, Jamie M and Ankner, John Francis and Kilbey, II, S Michael},
abstractNote = {Functional soft interfaces are of interest for a variety of technologies. We describe three methods for preparing substrates with alkyne groups, which show versatility for 'click' chemistry reactions. Two of the methods have the same root: formation of thin, covalently attached, reactive interfacial layers of poly(glycidyl methacrylate) (PGMA) via spin coating onto silicon wafers followed by reactive modification with either propargylamine or 5-hexynoic acid. The amine or the carboxylic acid moieties react with the epoxy groups of PGMA, creating interfacial polymer layers decorated with alkyne groups. The third method consists of using copolymers comprising glycidyl methacrylate and propargyl methacrylate (pGP). The pGP copolymers are spin coated and covalently attached on silicon wafers. For each method, we investigate the factors that control film thickness and content of alkyne groups using ellipsometry, and study the nanophase structure of the films using neutron reflectometry. Azide-terminated polymers of methacrylic acid and 2-vinyl-4,4-dimethylazlactone synthesized via reversible addition-fragmentation chain transfer polymerization were attached to the alkyne-modified substrates using 'click' chemistry, and grafting densities in the range of 0.007-0.95 chains nm{sup -2} were attained. The maximum density of alkyne groups attained by functionalization of PGMA with propargylamine or 5-hexynoic acid was approximately 2 alkynes nm{sup -3}. The alkyne content obtained by the three decorating approaches was sufficiently high that it was not the limiting factor for the click reaction of azide-capped polymers.},
doi = {10.1021/la2000798},
url = {https://www.osti.gov/biblio/1014237}, journal = {Langmuir},
issn = {0743-7463},
number = 10,
volume = 27,
place = {United States},
year = {2011},
month = {1}
}