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Investigation of Amphiphilic Polypeptoid-Functionalized Halloysite Nanotubes as Emulsion Stabilizer for Oil Spill Remediation

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    Research Article

    Investigation of Amphiphilic Polypeptoid-Functionalized Halloysite Nanotubes as Emulsion Stabilizer for Oil Spill Remediation
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    • Tianyi Yu
      Tianyi Yu
      Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge, Louisiana 70803, United States
      More by Tianyi Yu
    • Lauren T. Swientoniewski
      Lauren T. Swientoniewski
      Department of Biochemistry and Molecular Biology, Tulane University School of Medicine, New Orleans, Louisiana 70112, United States
      More by Lauren T. Swientoniewski
    • Marzhana Omarova
      Marzhana Omarova
      Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, Louisiana 70118, United States
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    • Mei-Chun Li
      Mei-Chun Li
      School of Renewable Natural Resources, Louisiana State University Agricultural Center, Baton Rouge, Louisiana 70803, United States
      More by Mei-Chun Li
    • Ioan I. Negulescu
      Ioan I. Negulescu
      Department of Textiles, Apparel Design and Merchandising, Louisiana State University, Baton Rouge, Louisiana 70803, United States
      More by Ioan I. Negulescu
    • Naisheng Jiang
      Naisheng Jiang
      Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge, Louisiana 70803, United States
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    • Omead A. Darvish
      Omead A. Darvish
      Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge, Louisiana 70803, United States
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    • Abhishek Panchal
      Abhishek Panchal
      Institute for Micromanufacturing, Louisiana Tech University, Ruston, Louisiana 71272, United States
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    • Diane A. Blake
      Diane A. Blake
      Department of Biochemistry and Molecular Biology, Tulane University School of Medicine, New Orleans, Louisiana 70112, United States
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      Orcidhttp://orcid.org/0000-0002-7532-1541
    • Qinglin Wu
      Qinglin Wu
      School of Renewable Natural Resources, Louisiana State University Agricultural Center, Baton Rouge, Louisiana 70803, United States
      More by Qinglin Wu
      Orcidhttp://orcid.org/0000-0001-5256-4199
    • Yuri M. Lvov
      Yuri M. Lvov
      Institute for Micromanufacturing, Louisiana Tech University, Ruston, Louisiana 71272, United States
      More by Yuri M. Lvov
      Orcidhttp://orcid.org/0000-0003-0722-5643
    • Vijay T. John
      Vijay T. John
      Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, Louisiana 70118, United States
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      Orcidhttp://orcid.org/0000-0001-5426-7585
    • Donghui Zhang*
      Donghui Zhang
      Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge, Louisiana 70803, United States
      *E-mail: [email protected]. Phone: 225-578-4893.
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      Orcidhttp://orcid.org/0000-0003-0779-6438
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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2019, 11, 31, 27944–27953
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    https://doi.org/10.1021/acsami.9b08623
    Published July 15, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Halloysite nanotubes (HNTs), naturally occurring and environmental benign clay nanoparticles, have been successfully functionalized with amphiphilic polypeptoid polymers by surface-initiated polymerization methods and investigated as emulsion stabilizers toward oil spill remediation. The hydrophilicity and lipophilicity balance (HLB) of the grafted polypeptoids was shown to affect the wettability of functionalized HNTs and their performance as stabilizers for oil-in-water emulsions. The functionalized HNTs having relatively high hydrophobic content (HLB = 12.0–15.0) afforded the most stable oil-in-water emulsions containing the smallest oil droplet sizes. This has been attributed to the augmented interfacial activities of polypeptoid-functionalized HNTs, resulting in more effective reduction of interfacial tension, enhancement of thermodynamic propensity of the HNT particles to partition at the oil–water interface, and increased emulsion viscosity relative to the pristine HNTs. Cell culture studies have revealed that polypeptoid-functionalized HNTs are noncytotoxic toward Alcanivorax borkumensis, a dominant alkane degrading bacterium found in the ocean after oil spill. Notably, the functionalized HNTs with higher hydrophobic polypeptoid content (HLB = 12.0–14.3) were shown to induce more cell proliferation than either pristine HNTs or those functionalized with less hydrophobic polypeptoids. It was postulated that the functionalized HNTs with higher hydrophobic polypeptoid content may promote the bacterial proliferation by providing larger oil–water interfacial area and better anchoring of bacteria at the interface.

    Copyright © 2019 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b08623.

    • Procedures for polypeptoid-grafted HNTs synthesis and characterization; synthetic procedures for cleaving polypeptoids from grafted-HNTs; TEM, cryo-S/TEM and energy-dispersive X-ray spectroscopy (EDS) sample preparation; experimental procedures for thermogravimetric analysis (TGA), surface tension, three-phase contact angle, steady shear and emulsion index measurements; resazurin assay and A. borkumensis cell culture procedure; 1H NMR spectrum of polymer that was cleaved off from g-HNTs by HF treatment; additional TGA, TEM, and cryo-TEM/SEM results as well as emulsion index (EI) and energy-dispersive X-ray spectroscopic (EDS) characterizations and cell growth study results (PDF)

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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2019, 11, 31, 27944–27953
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.9b08623
    Published July 15, 2019
    Copyright © 2019 American Chemical Society
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