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Design and Application of Photocrosslinkable Hydrogel Films for Fast and Efficient Decontamination of Chemical Warfare Agents
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    Design and Application of Photocrosslinkable Hydrogel Films for Fast and Efficient Decontamination of Chemical Warfare Agents
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    • Gabriela Toader
      Gabriela Toader
      Military Technical Academy ‘Ferdinand I’, 39-49 George Cosbuc Blvd., Bucharest050141, Romania
    • Raluca Elena Ginghina
      Raluca Elena Ginghina
      Research and Innovation Center for CBRN Defense and Ecology, 225 Oltenitei Blvd., Bucharest077160, Romania
    • Aurel Diacon*
      Aurel Diacon
      Military Technical Academy ‘Ferdinand I’, 39-49 George Cosbuc Blvd., Bucharest050141, Romania
      Faculty of Chemical Engineering and Biotechnologies, University POLITEHNICA of Bucharest, 1-7 Gh. Polizu Street, Bucharest011061, Romania
      *Email: [email protected]
      More by Aurel Diacon
    • Edina Rusen*
      Edina Rusen
      Faculty of Chemical Engineering and Biotechnologies, University POLITEHNICA of Bucharest, 1-7 Gh. Polizu Street, Bucharest011061, Romania
      *Email: [email protected]
      More by Edina Rusen
    • Adriana Elena Bratu
      Adriana Elena Bratu
      Research and Innovation Center for CBRN Defense and Ecology, 225 Oltenitei Blvd., Bucharest077160, Romania
      Faculty of Chemical Engineering and Biotechnologies, University POLITEHNICA of Bucharest, 1-7 Gh. Polizu Street, Bucharest011061, Romania
    • Alice Podaru
      Alice Podaru
      Military Technical Academy ‘Ferdinand I’, 39-49 George Cosbuc Blvd., Bucharest050141, Romania
      Faculty of Chemical Engineering and Biotechnologies, University POLITEHNICA of Bucharest, 1-7 Gh. Polizu Street, Bucharest011061, Romania
      More by Alice Podaru
    • Traian Rotariu
      Traian Rotariu
      Military Technical Academy ‘Ferdinand I’, 39-49 George Cosbuc Blvd., Bucharest050141, Romania
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    ACS Applied Polymer Materials

    Cite this: ACS Appl. Polym. Mater. 2023, 5, 1, 877–891
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    https://doi.org/10.1021/acsapm.2c01815
    Published December 20, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    This paper describes the design of photocrosslinkable interpenetrated network hydrogel peelable films, presenting the remarkable ability to successfully neutralize and safely remove from contaminated surfaces two of the most notorious highly toxic real chemical warfare agents (CWAs)─the blistering agent mustard gas (HD) and the nerve agent soman (GD). The goal of this study was to develop an innovative method for CWA decontamination that allows fast and efficient remediation of CWA-affected sites by entrapping the toxic compounds inside the polymeric matrix of the hydrogel, along with their efficient degradation using a dual route─hydrolytic and photocatalytic. With this aim, eight different formulations were developed for CWA decontamination involving aqueous blends containing the water-soluble components: a polymer (polyvinyl alcohol), monomers (acrylamide, acrylic acid, and/or 2-hydroxypropyl methacrylate in different molar ratios), a crosslinker (N,N′-methylenebisacrylamide), and a photoinitiator [2-hydroxy-4’-(2-hydroxyethoxy)-2-methylpropiphenone]. Also, in four of these decontamination solutions, titanium dioxide nanoparticles were incorporated to investigate if their photoactive potential can enhance the CWA decontamination process. The outstanding ability of these materials to neutralize CWA, as well as their suitability for decontamination purposes, was demonstrated through a variety of analytical tools (scanning electron microscopy, micro-CT, Fourier transform infrared spectroscopy, thermogravimetric analysis, dynamic mechanical analysis, and shear, tensile, and compression tests), swelling investigations, and gas chromatography–mass spectrometry surveyed decontamination tests on two real warfare agents (HD and GD) and one chemical warfare simulant (dimethyl methylphosphonate, a simulant for G series nerve agents). After peeling the hydrogels from the contaminated surfaces, the decontamination efficiency was calculated, and the values obtained varied from 99.35 to 99.98%.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsapm.2c01815.

    • Composition of the hydrogels employed for CWA decontamination; chemical structures of the hydrogels components and CWAs tested in the laboratory; proposed mechanism for the HD degradation in the hydrogels during the UV irradiation (blue─hydrolysis steps; red─free radicals generated species; and green─oxidative free radical steps); FTIR spectra of the neat hydrogels; decontamination hydrogels in the dry state and in their equilibrated swollen state; profiles of the swelling behavior of the decontamination hydrogels; SEM images of the hydrogels (cross-section view); micro-CT images of the hydrogels containing TiO2;Tg values from tan(δ) DMA plots; compression test; tensile test; synergistic hydrolytic and photocatalytic degradation of the CWA and the entrapment of the degradation products of the CWA inside the IPN of the crosslinked hydrogel film cured by UV radiation; results obtained for the tests performed on mustard gas (HD) decontamination from a metallic surface; results obtained for the tests performed on DMMP (as a simulant for GD) decontamination from a metallic surface; and chromatograms exemplifications (PDF)

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    This article is cited by 5 publications.

    1. Chuanyi Ma, Jian Li, Yi Wang, Zhanguo Li. Tough, self-healing, and freeze-resistant composite dual-network hydrogels for the decontamination of surface uranium (Ⅵ). Colloids and Surfaces A: Physicochemical and Engineering Aspects 2025, 705 , 135682. https://doi.org/10.1016/j.colsurfa.2024.135682
    2. Gabriela Toader, Raluca-Elena Ginghina, Adriana Elena Bratu, Alice Ionela Podaru, Daniela Pulpea, Traian Rotariu, Ana Mihaela Gavrilă, Aurel Diacon. Ionic Crosslinked Hydrogel Films for Immediate Decontamination of Chemical Warfare Agents. Gels 2024, 10 (7) , 428. https://doi.org/10.3390/gels10070428
    3. Aurel Diacon, Florin Albota, Alexandra Mocanu, Oana Brincoveanu, Alice Ionela Podaru, Traian Rotariu, Ahmad A. Ahmad, Edina Rusen, Gabriela Toader. Dual-Responsive Hydrogels for Mercury Ion Detection and Removal from Wastewater. Gels 2024, 10 (2) , 113. https://doi.org/10.3390/gels10020113
    4. Supharat Inphonlek, Chaiwat Ruksakulpiwat, Yupaporn Ruksakulpiwat. The Effect of Silver Nanoparticles/Titanium Dioxide in Poly(acrylic acid-co-acrylamide)-Modified, Deproteinized, Natural Rubber Composites on Dye Removal. Polymers 2024, 16 (1) , 92. https://doi.org/10.3390/polym16010092
    5. Gabriela Toader, Ionela Podaru, Edina Rusen, Aurel Diacon, Raluca Ginghina, Mioara Alexandru, Florina Zorila, Ana Gavrila, Bogdan Trica, Traian Rotariu, Mariana Ionita. Nafcillin-Loaded Photocrosslinkable Nanocomposite Hydrogels for Biomedical Applications. Pharmaceutics 2023, 15 (6) , 1588. https://doi.org/10.3390/pharmaceutics15061588

    ACS Applied Polymer Materials

    Cite this: ACS Appl. Polym. Mater. 2023, 5, 1, 877–891
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsapm.2c01815
    Published December 20, 2022
    Copyright © 2022 American Chemical Society

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