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基于β-环糊精/聚(N-乙酰苯胺)/石墨烯修饰电极的竞争主体客体相互作用的新型双重信号电化学传感策略:有机污染物的灵敏电化学测定。

A new dual-signalling electrochemical sensing strategy based on competitive host-guest interaction of a β-cyclodextrin/poly(N-acetylaniline)/graphene-modified electrode: sensitive electrochemical determination of organic pollutants.

机构信息

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, PR China.

出版信息

Chemistry. 2013 May 10;19(20):6368-73. doi: 10.1002/chem.201204635. Epub 2013 Mar 20.

Abstract

Based on the competitive host-guest interaction between a β-cyclodextrin/poly(N-acetylaniline)/electrogenerated-graphene (β-CD/PNAANI/EG) film and probe or target molecules, a new dual-signalling electrochemical sensing method has been developed for the sensitive and selective determination of organic pollutants. As a model system, rhodamine B (RhB) and 1-aminopyrene (1-AP) were adopted as the probe and target molecules, respectively. Due to the host-guest interaction, RhB molecules can enter into the hydrophobic inner cavity of β-CD, and the β-CD/PNAANI/EG-modified glassy carbon electrode displays a remarkable oxidation peak due to RhB. In the presence of 1-AP, competitive association to β-CD occurs and the RhB molecules are displaced by 1-AP. This results in a decreased oxidation peak current of RhB and the appearance of an oxidation peak current for 1-AP, and the changes of these signals correlate linearly with the concentration of 1-AP. When the value ΔI(1-AP)+∣ΔI(RhB)∣ (ΔI(1-AP) and ΔI(RhB) are the change values of the oxidation peak currents of 1-AP and RhB, respectively) is used as the response signal to quantitatively determine the concentration of 1-AP, the detection limit is much lower than that given by using ΔI(1-AP) or ΔI(RhB) as the response signal. This dual-signalling sensor can provide more sensitive target recognition and will have important applications in the sensitive and selective electrochemical determination of electroactive organic pollutants.

摘要

基于 β-环糊精/聚(N-乙酰苯胺)/电化学氧化石墨烯(β-CD/PNAANI/EG)薄膜与探针或目标分子之间的竞争主客体相互作用,开发了一种新的双信号电化学传感方法,用于灵敏和选择性地测定有机污染物。以罗丹明 B(RhB)和 1-氨基芘(1-AP)作为探针和目标分子的模型体系。由于主客体相互作用,RhB 分子可以进入β-CD 的疏水性内腔,并且β-CD/PNAANI/EG 修饰的玻碳电极由于 RhB 而显示出显著的氧化峰。在存在 1-AP 的情况下,发生与β-CD 的竞争缔合,并且 RhB 分子被 1-AP 取代。这导致 RhB 的氧化峰电流降低,并且出现 1-AP 的氧化峰电流,这些信号的变化与 1-AP 的浓度呈线性相关。当使用变化值ΔI(1-AP)+∣ΔI(RhB)∣(ΔI(1-AP)和ΔI(RhB)分别是 1-AP 和 RhB 的氧化峰电流的变化值)作为响应信号定量测定 1-AP 的浓度时,检测限比使用ΔI(1-AP)或ΔI(RhB)作为响应信号时低得多。这种双信号传感器可以提供更灵敏的目标识别,并且在电活性有机污染物的灵敏和选择性电化学测定中具有重要应用。

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