title: Cytosine derivatized bis(2,2'-bithienyl)methane molecularly imprinted polymer for selective recognition of 6-thioguanine, an antitumor drug.
abstract: A molecularly imprinted polymer (MIP) was designed and synthesized to serve as a functional material for selective recognition of 6-thioguanine (6TG), an antitumor drug. For that, the newly synthesized functional monomer, cytosine-bis(2,2'-bithienyl)-(4-carboxyphenyl)methane ester (Cyt-S4), revealed Watson-Crick type nucleobase pairing of 6TG. Formation of the Cyt-S4 and 6TG complex of the 2:1 stoichiometry was postulated based on the DFT calculations at the B3LYP/3-21G((⁎)) level and experimentally confirmed by fluorescence titration. The molecularly imprinted polymer (MIP) film was deposited by potentiodynamic electropolymerization on a Pt disk electrode as well as on an Au-coated glass slide and on an Au-quartz crystal resonator. The statistical model of formation of this film was successfully simulated by molecular dynamics. Completeness of the subsequent 6TG template extraction from MIP was confirmed by the UV-visible spectroscopy. An imprinting factor of 2.9 for the MIP film was determined by piezoelectric microgravimetry using ECQM. The double-layer capacity and alternating current measurements under flow-injection analysis (FIA) conditions were selected to transduce the 6TG recognition signal into the change of the double-layer capacity dependence on the 6TG concentration in solution for different supporting electrolyte concentrations. Detectability of the resulting chemosensor was 10 µM 6TG for the 0.5 M KF carrier solution in FIA. Selectivity of the chemosensor with respect to common interferences was high, e.g., it exceeded 130 to 2-amino-6-methylmercaptopurine, a 6TG metabolite.
authors: Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences (IPC PAS), Kasprzaka 44/52, 01-224 Warsaw, Poland; Department of Chemistry, University of North Texas, Denton, TX 76203-5017, USA.
authors: Tan-Phat
authors: TP
authors: Huynh
authors: Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences (IPC PAS), Kasprzaka 44/52, 01-224 Warsaw, Poland.
authors: Agnieszka
authors: A
authors: Wojnarowicz
authors: Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences (IPC PAS), Kasprzaka 44/52, 01-224 Warsaw, Poland; Department of Chemistry, University of North Texas, Denton, TX 76203-5017, USA.
authors: Marta
authors: M
authors: Sosnowska
authors: Faculty of Chemical Engineering, Israel Institute of Technology (TECHNION), Haifa 32000, Israel.
authors: Simcha
authors: S
authors: Srebnik
authors: Dipartimento di Scienza e Alta Tecnologia, Università degli Studi dell'Insubria, Via Valleggio 11, 22100 Como, Italy.
authors: Tiziana
authors: T
authors: Benincori
authors: Dipartimento di Chimica and C.I.Ma.I.NA, Università di Milano, Via Golgi 19, 20133 Milano, Italy.
authors: Francesco
authors: F
authors: Sannicolò
authors: Department of Chemistry, University of North Texas, Denton, TX 76203-5017, USA. Electronic address: Francis.Dsouza@unt.edu.
authors: Francis
authors: F
authors: D'Souza
authors: Department of Physical Chemistry of Supramolecular Complexes, Institute of Physical Chemistry, Polish Academy of Sciences (IPC PAS), Kasprzaka 44/52, 01-224 Warsaw, Poland; Faculty of Mathematics and Natural Sciences, School of Science, Cardinal Stefan Wyszynski University in Warsaw, Wóycickiego 1/3, 01-815 Warsaw, Poland. Electronic address: wkutner@ichf.edu.pl.
authors: Wlodzimierz
authors: W
authors: Kutner
mesh_terms: D000970:Antineoplastic Agents / Q000032:analysis / Q000737:chemistry; D003217:Conductometry / Q000295:instrumentation*; D003596:Cytosine / Q000737:chemistry*; D004867:Equipment Design; D019544:Equipment Failure Analysis; D054802:Molecular Imprinting / Q000379:methods*; D015203:Reproducibility of Results; D012680:Sensitivity and Specificity; D013499:Surface Properties; D013866:Thioguanine / Q000032:analysis* / Q000737:chemistry; D013876:Thiophenes / Q000737:chemistry*
chemical_list: D000970:Antineoplastic Agents; D013876:Thiophenes; C586225:bis(2,2'-bithien-5-yl)methane; D003596:Cytosine; D013866:Thioguanine
keywords: 6-thioguanine; Capacity measurement; Cytosine; Flow-injection analysis; Molecularly imprinted polymer