Aggregation-Suppressed Porous Processable Hexa-Zirconium/Polymer Composites for Detoxification of a Nerve Agent Simulant

Su, Shengyi; Jung, Dahee; Gong, Xinyi; Idrees, Karam B.; Hanna, Sylvia L.; İslamoğlu, Timur; Gianneschi, Nathan C.; Farha, Omar K.

doi:10.1021/acs.chemmater.2c00262

Cited by 10 publications

(16 citation statements)

References 43 publications

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“…UiO-66-NH 2 MOF materials considered as gold standard materials have t 1/2 ranging from 0.5 to 45 min in buffers having pH = 9−10. 14,27 A recent study by Su et al demonstrated DMNP degradation in borate buffer (pH = 8.04) with their best achieved t 1/2 ∼1 h. 37 Overall, the rates of reactivity obtained in the presented research are comparable to the aforementioned results and are potential candidates for inexpensive, scalable polymeric alternatives broadening the scope of applicable Chem-Bio protective materials. The halflives of DMNP, when exposed to all P4VP-Ox substrates, is further summarized in Figure 6a.…”

Section: ■ Results and Discussionsupporting

confidence: 72%

“…Overall, nanofiber materials fabricated upon electrospinning P4VP-OOx 20% provided the most rapid degradation kinetics with t 1/2 = 14.4 and 26.6 min using 53 and 27 mg of the substrate, respectively (bold values in Table ). UiO-66-NH 2 MOF materials considered as gold standard materials have t 1/2 ranging from 0.5 to 45 min in buffers having pH = 9–10. , A recent study by Su et al demonstrated DMNP degradation in borate buffer (pH = 8.04) with their best achieved t 1/2 ∼1 h . Overall, the rates of reactivity obtained in the presented research are comparable to the aforementioned results and are potential candidates for inexpensive, scalable polymeric alternatives broadening the scope of applicable Chem-Bio protective materials.…”

Section: Resultsmentioning

confidence: 99%

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Oxime-Functionalized, Nonwoven Nanofabrics for Rapid, Inexpensive Decontamination of a Nerve Agent Simulant

Biswas

Shuster

Baghirzade

et al. 2023

ACS Appl. Nano Mater.

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Organophosphorous-based nerve agents remain one of the most toxic and accessible chemical warfare agents known to man. Herein, we report the development of novel, oxime-functionalized poly(4-vinylpyridine) (P4VP-Ox) materials as inexpensive, scalable polymeric substrates capable of rapid decontamination of nerve agents, as demonstrated using one nerve agent simulant, dimethyl-4-nitrophenyl phosphate (DMNP). The incorporated oximes adjacent to positively charged pyridinium salts remain deprotonated at neutral to slightly basic pH, providing super-nucleophilic materials to deactivate nerve agents and their simulants rapidly and irreversibly. These materials were electrospun to form nanofabrics, providing increased surface area and enhanced reactivity for degradation of DMNP. Nanofibers obtained from P4VP functionalized at 20 mol % pendants with ortho-pyridinium oximes moieties (P4VP-OOx20%) provided the fastest reaction kinetics. This substrate provided complete decomposition of DMNP within 1.5 h and calculated t 1/2 = 14.4 min. The P4VP-Ox substrates were also found to be recyclable, allowing for quantitative DMNP degradation within 8 h over the course of four reaction cycles. Furthermore, to mimic real-life scenarios, we attempted solid-state DMNP degradation via applying small drops of DMNP directly on the nanofabric substrates and extracting with water for 31P NMR analysis. Overall, the P4VP-OOx20% substrate was found to retain its reactivity in the solid state, with the as-prepared nanofabric displaying >95% DMNP degradation after 6 h. When performed in different environments (i.e., 100% humidity, hexanes-rich atmosphere), the reactivity diminished slightly but still displayed >95% degradation after 24 h of reaction, establishing these materials for applications as reactive, economical, and easily scalable Chem-Bio protective materials.

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Section: ■ Results and Discussionsupporting

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Oxime-Functionalized, Nonwoven Nanofabrics for Rapid, Inexpensive Decontamination of a Nerve Agent Simulant

Biswas

Shuster

Baghirzade

et al. 2023

ACS Appl. Nano Mater.

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“…The 30 wt % Ce(OH) 4 -coated Matrimid (Ce(OH) 4 @Matrimid-Coat) and 30 wt % Zr(OH) 4 -coated Matrimid (Zr(OH) 4 @Matrimid-Coat) composites were fabricated by applying a solution containing NMP, chloroform, and ethanol in the ratio of 8:1:1, respectively, on the bare Matrimid to achieve a gel-like surface, after which brush was applied to create voids within the gel to improve the adhesion between the Matrimid substrate and the metal hydroxide particles. Following the formation of the gel-like composite, Ce(OH) 4 or Zr(OH) 4 particles were sprayed onto the surface of the polymer using the powder-spray gun and then dried at 40 °C for 48 h. In contrast, 30 wt % Ce(OH) 4 -coated PIM-1 (Ce(OH) 4 @PIM-1-Coat) and 30 wt % Zr(OH) 4 -coated PIM-1 (Zr(OH) 4 @PIM-1-Coat) composites were fabricated using the non-textured spray-coating technique (see Figure a) due to the low yield strength and toughness of PIM-1 . A mixture of DMF, ethanol, and chloroform (1:1:8) was applied to the surface of the bare PIM-1 polymer, after which 0.3 g of Ce(OH) 4 or Zr(OH) 4 was sprayed on the PIM-1’s wet surface and allowed to dry in a vacuum oven at 40 °C for 48 h.…”

Section: Methodsmentioning

confidence: 99%

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Aina,

Mondal,

Rownaghi

et al. 2024

ACS Appl. Eng. Mater.

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Polymer-based composites with tunable physiochemical properties are great candidates for efficient destruction of toxic chemicals and vapors. Herein, we report the development of metal hydoxide@polymer composites via matrix-incorporation and spray-coating methods and the assessment of the impact of different preparation methods on their physiochemical properties and detoxification performance. Specifically, Zr(OH) 4 and Ce(OH) 4 were used to enhance the catalytic activity of Ultem, Matrimid, and PIM-1 polymers toward hydrolysis of dimethyl 4-nitrophenylphosphonate (DMNP) simulant. Two different preparation techniques were employed to assess the structure-performance relations in the developed composites in terms of DMNP detoxification performance. The results obtained indicated that surface-coated metal hydoxide@polymer composites outperformed their respective incorporated analogues for both Zr(OH) 4 and Ce(OH) 4 due to the presence of more accessible surface active sites. Moreover, it was found that Ce(OH) 4 gave rise to a faster detoxification rate than Zr(OH) 4 in both matrix-incorporated and surfacecoated composites owing to higher Lewis acidity of Ce(OH) 4 than Zr(OH) 4 . Among the materials investigated, the best-performing material was found to be surface-coated Ce(OH) 4 @PIM-1, which exhibited the fastest DMNP detoxification rate of 0.08 min −1 and the shortest half-life of 8.67 min. The findings of this investigation highlight the potential of the spray-coating method for fabricating composites effective for detoxification of toxic chemicals and vapors.

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“…Organophosphorus nerve agents, including sarin, soman, and VX, are a class of the most toxic chemical warfare agents (CWAs) that can easily penetrate human mucosa to disrupt the central nervous system, resulting in constant muscle contraction and even death. , The use of organophosphorus nerve agents in terrorist attacks and assassination poses severe threats to human beings . In this context, there is a growing interest in developing effective materials/catalysts for degrading nerve agent stockpiles and for employment in personal protective equipment. − …”

Section: Introductionmentioning

confidence: 99%

MOF–Polymer Mixed Matrix Membranes as Chemical Protective Layers for Solid-Phase Detoxification of Toxic Organophosphates

Luo

Lin

Liu

et al. 2023

ACS Appl. Mater. Interfaces

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Zirconium-based metal–organic frameworks (Zr-MOFs) have been demonstrated as potent catalysts for the hydrolytic detoxification of organophosphorus nerve agents and their simulants. However, the practical implementation of these Zr-MOFs is limited by the poor processability of their powdered form and the necessity of water media buffered by a volatile liquid base in the catalytic reaction. Herein, we demonstrate the efficient solid-state hydrolysis of a nerve agent simulant (dimethyl-4-nitrophenyl phosphate, DMNP) catalyzed by Zr-MOF-based mixed matrix membranes. The mixed matrix membranes were fabricated by incorporating MOF-808 into the blending matrix of poly(vinylidene fluoride) (PVDF), poly(vinylpyrrolidone) (PVP), and imidazole (Im), in which MOF-808 provides highly active catalytic sites, the hydrophilic PVP helps to retain water for promoting the hydrolytic reaction, and Im serves as a base for catalytic site regeneration. Impressively, the mixed matrix membranes displayed excellent catalytic performance for the solid-state hydrolysis of DMNP under high humidity, representing a significant step toward the practical application of Zr-MOFs in chemical protective layers against nerve agents.

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Aggregation-Suppressed Porous Processable Hexa-Zirconium/Polymer Composites for Detoxification of a Nerve Agent Simulant

Cited by 10 publications

References 43 publications

Oxime-Functionalized, Nonwoven Nanofabrics for Rapid, Inexpensive Decontamination of a Nerve Agent Simulant

Oxime-Functionalized, Nonwoven Nanofabrics for Rapid, Inexpensive Decontamination of a Nerve Agent Simulant

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

MOF–Polymer Mixed Matrix Membranes as Chemical Protective Layers for Solid-Phase Detoxification of Toxic Organophosphates

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