Fabrication of device with poly(N-isopropylacrylamide)-b-ssDNA copolymer brush for resistivity study.

In this study, we grafted bromo-terminated poly(N-isopropylacrylamide) (PNIPAAm) brushes onto thin gold films deposited on silicon, and then reacted with NaN3 to produce azido-terminated PNIPAAm brushes. A probe sequence of single-stranded DNA (ssDNA) with a 4-pentynoic acid succinimidyl ester unit was grafted onto the azido-terminated PNIPAAm brushes through a click reaction, resulting in the formation of block copolymer brushes. The PNIPAAm-b-ssDNA copolymer brushes formed supramolecular complexes stabilized by bio-multiple hydrogen bonds (BMHBs), which enhanced the proton transfer and thereby decreased the resistivity of the structures. In addition, the optimal operation window for DNA detection ranges from 0 to 0.2 M of NaCl concentration. Therefore, the specimens were prepared in the PBS solution at 150 mM NaCl concentration for target hybridization. The supramolecular complex state of the PNIPAAm-b-ssDNA copolymer brushes transformed into the phase-separated state after the hybridization with 0.5 ng/µL of its target DNA sequence owing to the competition between BMHBs and complementary hydrogen bonds. This phase transformation of the PNIPAAm and probe segments inhibited the proton transfer and significantly increased the resistivity at 25 °C. Moreover, there were no significant changes in the resistivity of the copolymer brushes after hybridization with the target sequence at 45 °C. These results indicated that the phase-separated state of the PNIPAAm-b-ssDNA copolymer brushes, which was generally occurred above the LCST, can be substantially generated after hybridization with its target DNA sequence. By performing the controlled experiments, in the same manner, using another sequence with lengths similar to that of the target sequence without complementarity. In addition, the sequences featuring various degrees of complementarity were exploited to verify the phase separation behavior inside the PNIPAAm-b-ssDNA copolymer thin film.

Supermolecules of poly(N-isopropylacrylamide) complexating Herring sperm DNA with bio-multiple hydrogen bonding.

In this study we used the poly(N-isopropylacrylamide) (PNIPAAm) as a medium to blend with an organic DNA, herring sperm DNA (HSD), to generate PNIPAAm-HSD supramolecular complexes. Bio-multiple hydrogen bonding (BMHB) between PNIPAAm and HSD was investigated that changed the temperature responsiveness of PNIPAAm relatively to the HSD concentrations. With blending the HSD into PNIPAAm matrix, the phase separation in solution is completely opposite from that of neat PNIPAAm. Surface property in static water contact angle (SWCA) is also opposite from that of pure PNIPAAm upon increasing HSD content over 60%. In addition, we found that the PNIPAAm and HSD self-assembled a specific triangle-like structure at a PNIPAAm-to-HSD weight ratio of 1:4 at 25°C; while the triangle-like structure disappeared with increasing temperature to 45°C. Furthermore, both PNIPAAm and HSD could be regarded as insulator, but it transformed into a semiconductive matter after blending with the HSD. Incorporation of organic DNA with hydrogel could significantly change their properties, which might facilitate their use as novel materials in bioelectronics.