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通过氨基功能化 MOF 纳米片的酶反应检测新型荧光探针中的过氧化氢和葡萄糖。

Detection of hydrogen peroxide and glucose with a novel fluorescent probe by the enzymatic reaction of amino functionalized MOF nanosheets.

机构信息

Key Lab of Bioelectrochemistry & Environmental Analysis of Gansu, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, China.

出版信息

Anal Methods. 2021 Sep 30;13(37):4228-4237. doi: 10.1039/d1ay00190f.

Abstract

Amino-functionalized two-dimensional (2D) MOFs have great potential in biosensors due to their excellent water solubility, high fluorescence, large specific surface area, good adsorption properties and good ability to enrich the target analytes. Fluorescence detection of hydrogen peroxide and glucose mostly relies on monitoring the single fluorescence intensity changes in a single excitation wavelength. Here, a ratiometric fluorescence sensor based on NH-MIL-53(Al) nanosheets to sensitively detect HO and glucose through enzymatic reactions was developed. -Phenylenediamine (OPD) was oxidized by HO in the presence of horseradish peroxidase (HRP). Then, the oxidation product could be self-assembled on NH-MIL-53(Al) nanosheets by hydrogen bonding and π-π stacking. The orbital interaction or the fluorescence resonance energy transfer (FRET) between the nanosheets and the oxidation product could effectively quench the fluorescence of the nanosheets at 433 nm. At the same time, the oxidation product provided a new emission peak at 564 nm. The fluorescence ratio signal changes generated by this oxidation process were used to stably and sensitively detect HO and glucose. Structural and mechanistic analysis was carried out by calculation methods such as AICD and ORCA to explore the π electron structure characteristics, the hole/electron orbitals and the quenching phenomenon. The detection limit was 26.9 nM for HO and 0.041 μM for glucose. The detection of glucose in human serum has a satisfactory recovery of 97.4-102.8%. It is clear that the sensor has a good application prospect in real sample analysis.

摘要

氨基功能化二维(2D)MOFs 由于其出色的水溶性、高荧光性、大比表面积、良好的吸附性能和良好的富集目标分析物的能力,在生物传感器中具有巨大的潜力。过氧化氢和葡萄糖的荧光检测主要依赖于在单一激发波长下监测单一荧光强度变化。在这里,开发了一种基于 NH-MIL-53(Al)纳米片的比率荧光传感器,通过酶反应灵敏地检测 HO 和葡萄糖。在辣根过氧化物酶(HRP)存在下,邻苯二胺(OPD)被 HO 氧化。然后,氧化产物可以通过氢键和 π-π 堆积自组装在 NH-MIL-53(Al)纳米片上。纳米片和氧化产物之间的轨道相互作用或荧光共振能量转移(FRET)可以有效地猝灭纳米片在 433nm 处的荧光。同时,氧化产物在 564nm 处提供了一个新的发射峰。该氧化过程产生的荧光比率信号变化被用于稳定和灵敏地检测 HO 和葡萄糖。通过 AICD 和 ORCA 等计算方法进行结构和机理分析,以探讨π电子结构特性、空穴/电子轨道和猝灭现象。HO 的检测限为 26.9nM,葡萄糖的检测限为 0.041μM。人血清中葡萄糖的检测回收率为 97.4-102.8%,令人满意。显然,该传感器在实际样品分析中具有良好的应用前景。

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