Reactive ZIF‑LCrystal Surface for OrganophosphorousDegradation and Acetylcholinesterase Reactivation

The importance of crystal surface reactivity of reticular materials is exemplified by exfoliation of nonporous layered zeolitic imidazolate framework Zn­(mIm)<sub>2</sub>·0.5mImH (ZIF-L, mImH = 2-methylimidazole). Sonication of ZIF-L ethanolic suspensions leads to exfoliation of microcrystals along the 2 0 0 planes, giving rise to 1.5 μm wide × 25 nm thick flakes, which we term ZIF-L_exf. ZIF-L_exf exhibits a high reactivity toward hydrolytic degradation of extremely toxic G-type nerve agents, Soman (GD), and simulant diisopropylfluorophosphate (DIFP). The reactivity of the crystal surface of ZIF-L_exf toward P–F bond breakdown gives rise to framework structural degradation, releasing nucleophilic mImH molecules that reactivate organophosphate-inhibited acetylcholinesterase within 10 min. This detoxification process can be taken as a proof of concept for reversing organophosphorous poisoning. More generally, this approach underscores the importance of the crystal surface nature and composition to control the reactivity of reticular materials.

Publication Details

Journal
Figshare
Published
2025-03-11
DOI
https://doi.org/10.1021/jacs.5c00382.s001
Primary Topic
Metal-Organic Frameworks: Synthesis and Applications
Type
article
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Reactive ZIF‑LCrystal Surface for OrganophosphorousDegradation and Acetylcholinesterase Reactivation

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Metal-Organic Frameworks: Synthesis and Applications
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Reactive ZIF‑LCrystal Surface for OrganophosphorousDegradation and Acetylcholinesterase Reactivation

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Abstract

The importance of crystal surface reactivity of reticular materials is exemplified by exfoliation of nonporous layered zeolitic imidazolate framework Zn­(mIm)<sub>2</sub>·0.5mImH (ZIF-L, mImH = 2-methylimidazole). Sonication of ZIF-L ethanolic suspensions leads to exfoliation of microcrystals along the 2 0 0 planes, giving rise to 1.5 μm wide × 25 nm thick flakes, which we term ZIF-L_exf. ZIF-L_exf exhibits a high reactivity toward hydrolytic degradation of extremely toxic G-type nerve agents, Soman (GD), and simulant diisopropylfluorophosphate (DIFP). The reactivity of the crystal surface of ZIF-L_exf toward P–F bond breakdown gives rise to framework structural degradation, releasing nucleophilic mImH molecules that reactivate organophosphate-inhibited acetylcholinesterase within 10 min. This detoxification process can be taken as a proof of concept for reversing organophosphorous poisoning. More generally, this approach underscores the importance of the crystal surface nature and composition to control the reactivity of reticular materials.

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Metal-Organic Frameworks: Synthesis and Applications
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