Nicotine molecularly imprinted polymer: synergy of coordination and hydrogen bonding.
Nicotine molecularly imprinted polymer: synergy of coordination and hydrogen bonding.
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DOI：
10.1016/j.bios.2014.09.014
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发表时间：
2015-02
影响因子：
12.6
通讯作者：
T. Huynh;Chandra B K C;M. Sosnowska;J. Sobczak;V. Nesterov;F. D’Souza;W. Kutner
中科院分区：
文献类型：
--
作者：
T. Huynh;Chandra B K C;M. Sosnowska;J. Sobczak;V. Nesterov;F. D’Souza;W. Kutner
采用分子印迹技术合成了两个具有酞菁锌取代基（ZnPc-S16）和2-羟乙基取代基（EtOH-S4）的双（2,2′-二噻吩基）甲烷衍生物，作为功能单体用于尼古丁（Nic）的仿生识别。用密度泛函数理论在B3LYP/3-21 G / h水平上计算得到高的负吉布斯自由能增益ΔG= - 115.95 kJ/mol，并用氯仿紫外-可见滴定法测定了高的稳定常数Ks=4.67×105M−1，证实了ZnPc-S16和EtOH-S4在Nic模板中形成了预聚合配合物。利用该络合物溶液，通过动电位电聚合在EQCM石英晶体谐振器的Au电极上沉积了镍模板分子印迹聚合物（MIP-Nic）薄膜。印迹因子高达~9.9。用x射线光电子能谱（XPS）监测了MIP空腔对Nic分子的络合作用，发现在Nic模板后，ZnPc-S16的zn2 / p3/2电子的结合能发生了负位移。对于传感应用，在流动注射分析条件下进行同步计时安培法（CA）和压电微重力法（PM）测量。CA和PM的检出限分别低至40µM和12µM。其中，由于烟碱电氧化对Ag/AgCl的鉴别电位为1.10 V， CA化学感应对可替宁和肌氨酸的干扰具有更强的选择性。通过模拟Nic的络合作用来解释对分析物和干扰的选择性差异，并分别使用“冻结”的MIP-Nic分子腔来解释每种干扰。
Two new bis(2,2′-bithienyl)methane derivatives, one with the zinc phthalocyanine substituent (ZnPc-S16) and the other with the 2-hydroxyethyl substituent (EtOH-S4), were synthesized to serve as functional monomers for biomimetic recognition of nicotine (Nic) by molecular imprinting. Formation of a pre-polymerization complex of the Nic template with ZnPc-S16 and EtOH-S4 was confirmed by both the high negative Gibbs free energy gain, ΔG=−115.95 kJ/mol, calculated using the density functional theory at the B3LYP/3-21 G⁎ level, and the high stability constant,Ks=4.67×105M−1, determined by UV–vis titration in chloroform. A solution of this complex was used to deposit a Nic-templated molecularly imprinted polymer (MIP-Nic) film on an Au electrode of a quartz crystal resonator of EQCM by potentiodynamic electropolymerization. The imprinting factor was as high as ~9.9. Complexation of the Nic molecules by the MIP cavities was monitored with X-ray photoelectron spectroscopy (XPS), as manifested by a negative shift of the binding energy of the Zn 2p3/2electron of ZnPc-S16 after Nic templating. For sensing applications, simultaneous chronoamperometry (CA) and piezoelectric microgravimetry (PM) measurements were performed under flow-injection analysis conditions. The limit of detection of the CA and PM chemosensing was as low as 40 and 12 µM, respectively. Among them, the CA chemosensing was more selective to the cotinine and myosmine interferences due to the 1.10 V vs. Ag/AgCl discriminating potential of nicotine electro-oxidation applied. Differences in selectivity to the analyte and interferences were interpreted by modeling complexation of Nic and, separately, each of the interferences with a “frozen” MIP-Nic molecular cavity.