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

Abstract

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:

Coceancigh, Herman ^[1]; Tran-Ba, Khanh-Hoa ^[2]; Siepser, Natasha ^[3]; Baker, Lane A.  ^[3];

• Search DOE PAGES for author "Baker, Lane A."
• Search DOE PAGES for ORCID "0000-0001-5127-507X"

Ito, Takashi  ^[1]

• Search DOE PAGES for author "Ito, Takashi"
• Search DOE PAGES for ORCID "0000-0001-7443-3157"

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+ Show Author Affiliations

1. Department of Chemistry, Kansas State University, 213 CBC Building, Manhattan, Kansas 66506-0401, United States
2. Department of Chemistry, Kansas State University, 213 CBC Building, Manhattan, Kansas 66506-0401, United States, Department of Chemistry, Columbia University, New York, New York 10027, United States
3. Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, Indiana 47405, United States

Publication Date:

Tue Oct 10 00:00:00 EDT 2017

Research Org.:

Kansas State Univ., Manhattan, KS (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:

1398835

Alternate Identifier(s):

OSTI ID: 1413282

Grant/Contract Number:  

SC0002362

Resource Type:

Published Article

Journal Name:

Langmuir

Additional Journal Information:

Journal Name: Langmuir Journal Volume: 33 Journal Issue: 43; Journal ID: ISSN 0743-7463

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY