Nicotine molecularly imprinted polymer: Synergy of coordination and hydrogen bonding

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, Delta G=-115.95 kJ/mol, calculated using the density functional theory at the B3LYP/3-21 G* level, and the high stability constant, K-s, =4.67 x 10(5) M-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 2p(3/2) electron 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 mu M, 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. (C) 2014 Elsevier B.V. All rights reserved.