A novel bio-based polycationic polyurethane as an ion-selective membrane for nitrate sensing was successfully developed. In this work, the intermolecular interactions at active polymeric sites play a primary role in selective nitrate-ion detection. From the experiment, FTIR shows a significant shift from 1543 cm −1 to 1548 cm −1 in N-H bending, indicating that intermolecular interactions occur between the polycationic polyurethane and nitrate. AFM shows that the surface roughness of the polycationic polyurethane decreases from 95.7 nm to 12.2 nm after immersion in nitrate solution. Meanwhile, FESEM images show that the bright area, which represents the hard segment of polycationic polyurethane, decreases after immersion, indicating that the nitrate is interacting with the hard segment of the polycationic polyurethane via intermolecular interaction. Furthermore, EIS shows that the conductivity increases from 2.84 × 10 −11 to 5.34 × 10 −11 S cm −1 after ion exchange occurs between the iodide and nitrate on the polycationic polyurethane. To assess the sensing performance, the sensor probe is fabricated by coating the polycationic polyurethane thin film on the tapered region of an optical fiber. Rapid detection, good repeatability, and a sensitivity of 5.94 × 10 −2 µW/ppm are obtained for nitrate detection using the above bio-based-sensing material. The selectivity study also shows that the sensing material possesses high affinity toward the nitrate ion.
Ferrocene or ferrocenium has been widely studied in the field of organometallic complexes because of its stable thermodynamic, kinetic and redox properties. Novel hexaferrocenium tri[hexa(isothiocyanato)iron(III)]trihydroxonium (HexaFc) complex was the product from the reaction of ferrocene, maleic acid and ammonium thiocyanate and was confirmed by elemental analysis CHNS, FTIR and single crystal X-ray crystallography. In this study, HexaFc was used for the first time as an electroactive indicator for porcine DNA biosensor. The UV–Vis DNA titrations with this compound showed hypochromism and redshift at 250 nm with increasing DNA concentrations. The binding constant (Kb) for HexaFc complex towards CT-DNA (calf-thymus DNA) was 3.1 × 104 M−1, indicated intercalator behaviour of the complex. To test the usefulness of this complex for DNA biosensor application, a porcine DNA biosensor was constructed. The recognition probes were covalently immobilised onto silica nanospheres (SiNSs) via glutaraldehyde linker on a screen-printed electrode (SPE). After intercalation with the HexaFc complex, the response of the biosensor to the complementary porcine DNA was measured using differential pulse voltammetry. The DNA biosensor demonstrated a linear response range to the complementary porcine DNA from 1 × 10−6 to 1 × 10−3 µM (R2 = 0.9642) with a limit detection of 4.83 × 10−8 µM and the response was stable up to 23 days of storage at 4 °C with 86% of its initial response. The results indicated that HexaFc complex is a feasible indicator for the DNA hybridisation without the use of a chemical label for the detection of porcine DNA.
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