基於雙鎳二硫代烯的金屬有機骨架結構的合成
作者：
小柯機器人發布時間：2020/11/18 13:09:04
南京大學左景林團隊研究了一種基於雙鎳二硫代烯的金屬有機骨架結構的合成，晶體結構，及其作為電化學葡萄糖傳感器的應用。 這一研究成果於2020年11月13日發表在國際頂尖學術期刊《美國化學會志》。
將氧化還原活性四硫富瓦烯(TTF)核與金屬配位基團功能化，為有機-無機雜化材料的結構調控和電子性能提供了新的前景。
為了擴展這一概念，研究團隊合成了雙鎳（二硫代烯二苯甲酸）[Ni(C2S2(C6H4COOH)2)2]，它可以被認為是有機四硫富瓦烯四苯甲酸（H4TFTB）的無機類似物。同樣，[Ni(C2S2(C6H4COOH)2)2]是一種新型功能金屬-有機框架的氧化還原活性連接劑，如該文通過[Mn2{Ni(C2S2(C6H4COO)2)2}(H2O)2]·2DMF， (1, DMF = N,N-二甲基甲醯胺)的合成所證實。1與報導的[Mn2(TTFTB)(H2O)2](2)同構，但由於[NiS4]核心的多重氧化-還原狀態，使葡萄糖被高氧化態[NiS4]中心氧化為葡萄糖內酯，因此是一種更好的電化學葡萄糖傳感器。
採用一步水熱法合成了1-CF，作為一種非酶葡萄糖傳感器，具有良好的電化學性能。製備的1-CF電極靈敏度為27.9A M–1 cm–2，線性檢測範圍從2.0×10-6到2.0×10-3M，檢測下限為1.0×10-7M（信噪比為3），穩定性和重現性令人滿意。
附：英文原文
Title: A Metal–Organic Framework Based on a Nickel Bis(dithiolene) Connector: Synthesis, Crystal Structure, and Application as an Electrochemical Glucose Sensor
Author: Yan Zhou, Qin Hu, Fei Yu, Guang-Ying Ran, Hai-Ying Wang, Nicholas D. Shepherd, Deanna M. D』Alessandro, Mohamedally Kurmoo, Jing-Lin Zuo
Issue&Volume: November 13, 2020
Abstract: Functionalizing the redox-active tetrathiafulvalene (TTF) core with groups capable of coordination to metals provides new perspectives on the modulation of architectures and electronic properties of organic–inorganic hybrid materials. With a view to extending this concept, we have now synthesized nickel bis(dithiolene-dibenzoic acid), [Ni(C2S2(C6H4COOH)2)2], which can be considered as the inorganic analogue of the organic tetrathiafulvalene-tetrabenzoic acid (H4TTFTB). Likewise, [Ni(C2S2(C6H4COOH)2)2] is a redox-active linker for new functional metal–organic frameworks, as demonstrated here with the synthesis of [Mn2{Ni(C2S2(C6H4COO)2)2}(H2O)2]·2DMF, (1, DMF = N,N-dimethylformamide). 1 is isomorphic to the reported [Mn2(TTFTB)(H2O)2] (2) but is a better electrochemical glucose sensor due to the multiple oxidation–reduction states of the [NiS4] core, which allow glucose to be oxidized to glucolactone by the high oxidation state [NiS4] center. As a non-enzymatic glucose sensor, 1 on Cu foam (CF), 1-CF, was synthesized by a one-step hydrothermal method and exhibited an excellent electrochemical performance. The fabricated 1-CF electrode offers a high sensitivity of 27.9 A M–1 cm–2, with a wide linear detection range from 2.0 × 10–6 to 2.0 × 10–3 M, a low detection limit of 1.0 × 10–7 M (signal/noise = 3), and satisfactory stability and reproducibility.
DOI: 10.1021/jacs.0c09009
Source: https://pubs.acs.org/doi/10.1021/jacs.0c09009