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绿色 MIP-202(Zr) 催化剂:神经毒剂的降解和热稳定仿生传感。

Green MIP-202(Zr) Catalyst: Degradation and Thermally Robust Biomimetic Sensing of Nerve Agents.

机构信息

Department of Nanoengineering, University of California, San Diego, La Jolla, California 92093, United States.

Bennett Aerospace, 1100 Crescent Green, No. 250, Cary, North Carolina 27518, United States.

出版信息

J Am Chem Soc. 2021 Nov 3;143(43):18261-18271. doi: 10.1021/jacs.1c08356. Epub 2021 Oct 22.

Abstract

Rapid and robust sensing of nerve agent (NA) threats is necessary for real-time field detection to facilitate timely countermeasures. Unlike conventional phosphotriesterases employed for biocatalytic NA detection, this work describes the use of a new, green, thermally stable, and biocompatible zirconium metal-organic framework (Zr-MOF) catalyst, MIP-202(Zr). The biomimetic Zr-MOF-based catalytic NA recognition layer was coupled with a solid-contact fluoride ion-selective electrode (F-ISE) transducer, for potentiometric detection of diisopropylfluorophosphate (DFP), a F-containing G-type NA simulant. Catalytic DFP degradation by MIP-202(Zr) was evaluated and compared to the established UiO-66-NH catalyst. The efficient catalytic DFP degradation with MIP-202(Zr) at near-neutral pH was validated by P NMR and FT-IR spectroscopy and potentiometric F-ISE and pH-ISE measurements. Activation of MIP-202(Zr) using Soxhlet extraction improved the DFP conversion rate and afforded a 2.64-fold improvement in total percent conversion over UiO-66-NH. The exceptional thermal and storage stability of the MIP-202/F-ISE sensor paves the way toward remote/wearable field detection of G-type NAs in real-world environments. Overall, the green, sustainable, highly scalable, and biocompatible nature of MIP-202(Zr) suggests the unexploited scope of such MOF catalysts for on-body sensing applications toward rapid on-site detection and detoxification of NA threats.

摘要

快速而强大的神经毒剂 (NA) 威胁感测对于实时现场检测是必要的,以方便及时采取对策。与用于生物催化 NA 检测的传统膦酸酯酶不同,这项工作描述了使用一种新的、绿色的、热稳定的和生物相容的锆金属有机骨架 (Zr-MOF) 催化剂 MIP-202(Zr)。仿生 Zr-MOF 基催化 NA 识别层与固态接触氟离子选择性电极 (F-ISE) 换能器耦合,用于对二异丙基氟膦 (DFP) 的电位检测,DFP 是一种含氟 G 型 NA 模拟物。评估了 MIP-202(Zr)对 DFP 的催化降解作用,并与已建立的 UiO-66-NH 催化剂进行了比较。通过 P NMR 和 FT-IR 光谱以及电位 F-ISE 和 pH-ISE 测量验证了 MIP-202(Zr)在近中性 pH 下高效催化 DFP 降解的能力。使用索氏提取激活 MIP-202(Zr)提高了 DFP 的转化率,并使总转化率相对于 UiO-66-NH 提高了 2.64 倍。MIP-202/F-ISE 传感器具有出色的热稳定性和存储稳定性,为在实际环境中对 G 型 NAs 进行远程/可穿戴现场检测铺平了道路。总的来说,MIP-202(Zr) 的绿色、可持续、高度可扩展和生物相容性表明,这种 MOF 催化剂在用于快速现场检测和解毒 NA 威胁的身体传感器应用方面具有未被开发的潜力。

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