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钐掺杂磷酸铈纳米棒的结构依赖性发光、过氧化物模拟酶活性及过氧化氢传感性能

Structure dependent luminescence, peroxidase mimetic and hydrogen peroxide sensing of samarium doped cerium phosphate nanorods.

作者信息

Vinothkumar G, I L Arun, Arunkumar P, Ahmed Waseem, Ryu Sangbong, Cha Suk Won, Babu K Suresh

机构信息

Centre for Nanoscience and Technology, Madanjeet School of Green Energy Technology, Pondicherry University, R. V. Nagar, Kalapet, Puducherry - 605 014, India.

出版信息

J Mater Chem B. 2018 Nov 7;6(41):6559-6571. doi: 10.1039/c8tb01643g. Epub 2018 Sep 24.

Abstract

Rare earth phosphates have been used extensively in luminescent phosphors, bio-imaging, catalysis, and sensors. However, there is a need to correlate the structural-chemical changes associated with stability and performance. In the present work, hydrothermally synthesized CePO:Sm (x = 0, 5 and 10 mol%) nanorods were annealed at different temperatures to understand the modulations in structure as well as optical and enzyme mimetic properties. As prepared samarium doped cerium phosphate (SCP) nanorods crystallized in a hydrated hexagonal structure transformed into an anhydrous hexagonal and a monoclinic structure on annealing at 400 °C and 800 °C, respectively. Though temperature did not affect the rod-like morphology of the SCP, the lattice strain changed from compressive to tensile. Monoclinic SCP exhibited excellent emission until 5% Sm doping while the quenching effect dominated at 10% Sm. Monoclinic SCP samples demonstrated higher peroxidase-like enzymatic activity in comparison to natural enzyme HRP and hexagonal SCP. A mechanism for the enhanced peroxidase-like activity of the monoclinic structure was proposed based on the fluorescence property of terephthalic acid and the surface peroxo complex using Raman spectroscopy. Fluorimetric detection based on the luminescent quenching effect of the monoclinic SCP nanorods treated with different concentrations of hydrogen peroxide showed a linear response from 0 to150 μM concentration with a detection limit (LOD) of 3.17 μM HO. Our results demonstrate the importance of structure for enzyme mimetic activity.

摘要

稀土磷酸盐已广泛应用于发光磷光体、生物成像、催化和传感器领域。然而,有必要将与稳定性和性能相关的结构化学变化关联起来。在本工作中,对水热合成的CePO:Sm(x = 0、5和10 mol%)纳米棒在不同温度下进行退火处理,以了解其结构以及光学和类酶性质的调制情况。制备的掺钐磷酸铈(SCP)纳米棒结晶为水合六方结构,分别在400 °C和800 °C退火后转变为无水六方结构和单斜结构。尽管温度不影响SCP的棒状形态,但晶格应变从压缩变为拉伸。单斜SCP在5% Sm掺杂之前表现出优异的发光,而在10% Sm时猝灭效应占主导。与天然酶HRP和六方SCP相比,单斜SCP样品表现出更高的过氧化物酶样酶活性。基于对苯二甲酸的荧光性质和使用拉曼光谱的表面过氧配合物,提出了单斜结构增强过氧化物酶样活性的机制。基于不同浓度过氧化氢处理的单斜SCP纳米棒的发光猝灭效应进行的荧光检测显示,在0至150 μM浓度范围内呈线性响应,检测限(LOD)为3.17 μM HO。我们的结果证明了结构对类酶活性的重要性。

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