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Title: Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using an Electrochemically Assisted Click Reaction

Here in this study, the longitudinally controlled modification of the inner surfaces of poly(ethylene terephthalate) (PET) track-etched pores was explored using an electrochemically assisted Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) click reaction. Cylindrical or conical PET track-etched pores were first decorated with ethynyl groups via the amidation of surface -COOH groups, filled with a solution containing Cu(II) and azide-tagged fluorescent dye, and then sandwiched between comb-shaped and planar gold electrodes. Cu(I) was produced at the comb-shaped working electrode by the reduction of Cu(II); it diffused along the pores toward the other electrode and catalyzed CuAAC between an azide-tagged fluorescent dye and a pore-tethered ethynyl group. The modification efficiency of cylindrical pores (ca. 1 μm in diameter) was assessed from planar and cross-sectional fluorescence microscope images of modified membranes. Planar images showed that pore modification took place only above the teeth of the comb-shaped electrode with a higher reaction yield for longer Cu(II) reduction times. Cross-sectional images revealed micrometer-scale gradient modification along the pore axis, which reflected a Cu(I) concentration profile within the pores, as supported by finite-element computer simulations. The reported approach was applicable to the asymmetric modification of cylindrical pores with two different fluorescent dyes in the opposite directions and alsomore » for the selective visualization of the tip and base openings of conical pores (ca. 3.5 μm in base diameter and ca. 1 μm in tip diameter). Lastly, the method based on electrochemically assisted CuAAC provides a controlled means to fabricate asymmetrically modified nanoporous membranes and, in the future, will be applicable for chemical separations and the development of sequential catalytic reactors.« less
Authors:
 [1] ;  [2] ;  [3] ; ORCiD logo [3] ; ORCiD logo [1]
  1. Kansas State Univ., Manhattan, KS (United States). Dept. of Chemistry
  2. Kansas State Univ., Manhattan, KS (United States). Dept. of Chemistry; Columbia Univ., New York, NY (United States). Dept. of Chemistry
  3. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
SC0002362
Type:
Published Article
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 43; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Research Org:
Kansas State Univ., Manhattan, KS (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1398835
Alternate Identifier(s):
OSTI ID: 1413282

Coceancigh, Herman, Tran-Ba, Khanh-Hoa, Siepser, Natasha, Baker, Lane A., and Ito, Takashi. Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using an Electrochemically Assisted Click Reaction. United States: N. p., Web. doi:10.1021/acs.langmuir.7b02778.
Coceancigh, Herman, Tran-Ba, Khanh-Hoa, Siepser, Natasha, Baker, Lane A., & Ito, Takashi. Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using an Electrochemically Assisted Click Reaction. United States. doi:10.1021/acs.langmuir.7b02778.
Coceancigh, Herman, Tran-Ba, Khanh-Hoa, Siepser, Natasha, Baker, Lane A., and Ito, Takashi. 2017. "Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using an Electrochemically Assisted Click Reaction". United States. doi:10.1021/acs.langmuir.7b02778.
@article{osti_1398835,
title = {Longitudinally Controlled Modification of Cylindrical and Conical Track-Etched Poly(ethylene terephthalate) Pores Using an Electrochemically Assisted Click Reaction},
author = {Coceancigh, Herman and Tran-Ba, Khanh-Hoa and Siepser, Natasha and Baker, Lane A. and Ito, Takashi},
abstractNote = {Here in this study, the longitudinally controlled modification of the inner surfaces of poly(ethylene terephthalate) (PET) track-etched pores was explored using an electrochemically assisted Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) click reaction. Cylindrical or conical PET track-etched pores were first decorated with ethynyl groups via the amidation of surface -COOH groups, filled with a solution containing Cu(II) and azide-tagged fluorescent dye, and then sandwiched between comb-shaped and planar gold electrodes. Cu(I) was produced at the comb-shaped working electrode by the reduction of Cu(II); it diffused along the pores toward the other electrode and catalyzed CuAAC between an azide-tagged fluorescent dye and a pore-tethered ethynyl group. The modification efficiency of cylindrical pores (ca. 1 μm in diameter) was assessed from planar and cross-sectional fluorescence microscope images of modified membranes. Planar images showed that pore modification took place only above the teeth of the comb-shaped electrode with a higher reaction yield for longer Cu(II) reduction times. Cross-sectional images revealed micrometer-scale gradient modification along the pore axis, which reflected a Cu(I) concentration profile within the pores, as supported by finite-element computer simulations. The reported approach was applicable to the asymmetric modification of cylindrical pores with two different fluorescent dyes in the opposite directions and also for the selective visualization of the tip and base openings of conical pores (ca. 3.5 μm in base diameter and ca. 1 μm in tip diameter). Lastly, the method based on electrochemically assisted CuAAC provides a controlled means to fabricate asymmetrically modified nanoporous membranes and, in the future, will be applicable for chemical separations and the development of sequential catalytic reactors.},
doi = {10.1021/acs.langmuir.7b02778},
journal = {Langmuir},
number = 43,
volume = 33,
place = {United States},
year = {2017},
month = {9}
}