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