Molecularly Imprinted Polymer for Recognition of 5-Fluorouracil by RNA-type Nucleobase Pairing

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• 作者：Tan-Phat Huynh ; Piotr Pieta ; Francis D鈥橲ouza ; Wlodzimierz Kutner
• 刊名：Analytical Chemistry
• 出版年：2013
• 出版时间：September 3, 2013
• 年：2013
• 卷：85
• 期：17
• 页码：8304-8312
• 全文大小：410K
• 年卷期：v.85,no.17(September 3, 2013)
• ISSN：1520-6882

文摘

A 6-aminopurine (adenine) derivative of bis(2,2鈥?bithienyl)methane, vis., 4-[2-(6-amino-9H-purin-9-yl)ethoxy]phenyl-4-[bis(2,2鈥?bithienyl)methane] or Ade-BTM, was designed and synthesized for recognition of 5-fluorouracil (FU), an antitumor chemotherapy agent, by RNA-type (nucleobase pairing)-driven molecular imprinting. The prepolymerization complex stoichiometry involved one FU molecule and two molecules of the Ade-BTM functional monomer. Molecular structure of this complex was thermodynamically optimized via density functional theory at the B3LYP/3-21G* level. The stability constant of the FU鈥揂de-BTM complex of 1:2 stoichiometry was K = 2.17(卤0.07) 脳 10⁷ M^鈥?, as determined by titration with quenching of fluorescence of the bis(2,2鈥?bithienyl)methane moiety of Ade-BTM by the FU titrant, in benzonitrile, at 352 nm excitation. Next, (5-fluorouracil)-templated molecularly imprinted polymer (MIP-FU) films were deposited on indium鈥搕in oxide (ITO) or Au film-coated glass slides, Pt disk electrodes, or 10-MHz quartz crystal resonators by potentiodynamic electropolymerization from solution of FU, Ade-BTM, and tris([2,2鈥?bithiophen]-5-yl)methane (TTM) cross-linking monomer at FU:Ade-BTM:TTM = 1:2:3 mol ratio. Then UV鈥搗isible and Fourier transform infrared (FT-IR) spectra of the MIP-FU films were recorded to confirm the FU template presence in the MIP-FU film and its subsequent release by extraction with methanol from this film. For determination of the stability constant of the complex of the MIP cavity and FU, piezoelectric microgravimetry (PM) under both batch- and flow-injection analysis conditions was used. For sensing application, three different transduction platforms [differential pulse voltammetry (DPV), capacitive impedimetry (CI), and PM] were integrated with the MIP-FU recognition unit. The limit of detection (LOD) was 56 nM, 75 nM, and 0.26 mM, for these chemosensors, respectively, indicating suitability of the former two for FU determination in blood plasma or serum (500 nM). Moreover, the CI chemosensor was appreciably more sensitive to FU than to their common interferences.