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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
 [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:
Published Article
Journal Name:
Additional Journal Information:
Journal Volume: 33; Journal Issue: 43; Journal ID: ISSN 0743-7463
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
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Alternate Identifier(s):
OSTI ID: 1413282