aeChemosensing systems were devised for the enantioselective determination of D-and L-phenylalanine (D-and L-Phe). As recognition units of these systems, molecularly imprinted polymers (MIPs) were designed, guided by DFT calculations, and then synthesized. For the preparation of these MIPs, carboxy derivatized bis(bithiophene) was used as the functional monomer. Both templated and templateextracted MIP films as well as non-imprinted polymer (NIP) films were characterized by IR spectroscopy to prove Phe templation, and then extraction. Extended-gate field-effect transistors (EG-FETs) served as transducers. The EG-FET gates were coated with D-or (L-Phe)-templated MIP films, by electropolymerization, to result in complete chemosensors. These chemosensors rapidly and selectively responded to D-and L-Phe enantiomer analytes. They readily discriminated between a homologous series of analytes differing by a single atom as well as pairs of enantiomers differing in their three-dimensional structures. Linear dynamic concentration ranges for D-and L-Phe extended from 13 to 100 mM. For both Phe enantiomers, the limit of detection was 13 mM. The enantioselectivity factor was B2.3 for both chemosensors.
We devised and fabricated a chemosensor for determination of the genetically relevant 5'-GCGGCGGC-3' (G = guanine; C = cytosine) oligonucleotide. For that, we simultaneously electrosynthesized and electrode-immobilized a sequence-defined octakis(2,2'-bithien-5-yl) DNA hybridizing probe using both a "macromolecular imprinting in polymer strategy" and a sequence-programmable peptide nucleic acid (PNA) template. With electrochemical impedance spectroscopy (EIS) and surface plasmon resonance (SPR) transductions under stagnant-solution and flow injection analysis (FIA) conditions, respectively, we determined the above oligonucleotide with 200-pM EIS limit of detection. With its EIS-determined apparent imprinting factor of ∼4.0, the chemosensor was discriminative to both mismatched oligonucleotides and Dulbecco's modified Eagle's medium sample interferences.
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