Anion-Exchange-Based Amperometric Assay for Heparin Using Polyimidazolium as Synthetic Receptor

Anion-Exchange-Based Amperometric Assay for Heparin Using Polyimidazolium as Synthetic Receptor
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使用聚咪唑作为合成受体的基于阴离子交换的肝素安培分析

DOI:
10.1021/ac400201c
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发表时间:
2013-03-19
影响因子:
7.4
通讯作者:
Mao, Lanqun
Mao, Lanqun
中科院分区:
化学1区
文献类型:
--
作者:
Qi, Hetong;Zhang, Li;Mao, Lanqun

文献摘要

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本研究证明了一种简便而有效的电化学活性肝素的安培分析策略的基础上的阴离子交换机制与聚咪唑(PIM)作为合成受体。安培肝素测定的基本原理基本上是基于合成Pim受体对电化学活性铁氰化物(Fe(CN)(6)(3-))和电化学非活性肝素的不同结合亲和力。为了完成电流分析,首先合成Pim并用作人工受体以识别阴离子(即,Fe(CN)(6)(3-)和肝素)。合成的Pim受体对肝素的结合亲和力比对Fe(CN)(6)(3-)的结合亲和力更强,这基本上验证了通过阴离子交换机制的安培肝素测定法,其中吸附在Pim膜上的Fe(CN)(6)(3-)的氧化还原峰电流的降低作为信号读出。用循环伏安法、傅里叶变换红外光谱和紫外-可见光谱证实了Fe(CN)(6)(3-)与肝素在Pim受体上的阴离子交换。电流降低的比率显示出与肝素浓度的线性关系,浓度范围为0.5至10 μ M。通过动物腹腔给药和采集血清样品的实验,证明该方法对研究肝素在生物系统中的代谢具有潜在的有用性。本研究不仅提供了一种简单而有效的肝素分析方法,而且通过充分利用超分子原理,为电化学惰性物种的安培分析方法的发展开辟了一条新的途径。
This study demonstrates a facile yet effective strategy for amperometric assay of electrochemically inactive heparin based on an anion-exchange mechanism with polyimidazolium (Pim) as the synthetic receptor. The rationale for the amperometric heparin assay is essentially based on the different binding affinity of the synthetic Pim receptor toward electrochemically active ferricyanide (Fe(CN)(6)(3-)) and electrochemically inactive heparin. To accomplish the amperometric assay, Pim is first synthesized and used as the artificial receptor to recognize the anions (i.e., Fe(CN)(6)(3-) and heparin). The stronger binding affinity of the synthetic Pim receptor toward heparin than toward Fe(CN)(6)(3-) essentially validates the amperometric heparin assay through an anion-exchange mechanism with the decrease in the redox peak current of Fe(CN)(6)(3-) adsorbed onto the Pim film as the signal readout. The anion exchange between Fe(CN)(6)(3-) and heparin on the Pim receptor is verified by cyclic voltammetry and Fourier transform IR and UV-visible spectroscopies. The ratio of the current decrease shows a linear relationship with heparin concentration with a concentration range from 0.5 to 10 mu M. With animal experiments by dosing intraperitoneally and collecting the serum sample, the method is demonstrated to be potentially useful for investigating heparin metabolism in the biological system. This study not only provides a simple yet effective route to a heparin assay but also opens a new way to developing amperometric methods for electrochemically inert species by fully utilizing the supramolecular principles.