The impedimetric sensing of DNA hybridization on polyaniline/polyacrylate (PANI/PAA)-modified boron-doped diamond (BDD) electrode has been investigated. An ultrathin film of PANI-PAA copolymer was electropolymerized onto the diamond surfaces to provide carboxylic groups for tethering to DNA sensing probes. The electrochemical impedance and the intrinsic electroactivity of the polymer-diamond interface were analyzed after the hybridization reaction with target and non-target DNA. The impedance measurement shows changes in the impedance modulus as well as electron-transfer resistance at the stage of probe DNA immobilization (single-strand), as well as after hybridization with target DNA (double-strand). DNA hybridization increases the capacitance of the polymer-DNA layer and reduces the overall impedance of the DNA-polymer-diamond stack significantly. The polymer-modified BDD electrode shows no detectable nonspecific adsorption, with good selectivity between the complementary DNA targets and the one-base mismatch targets. The detection limit was measured to be 2 x 10(-8) M at 1000 Hz. Denaturing test on the hybridized probe and subsequent reuse of the probe indicates chemical robustness of the sensor. Our results suggest that electropolymerization followed by the immobilization of biomolecules is a simple and effective way of creating a functional biomolecular scaffold on the diamond surface. In addition, label-free electrochemical impedance method can provide direct and noninvasive sensing of DNA hybridization on BDD.
We have synthesized edge-oriented MoS2 nanosheets by the evaporation of a single source precursor based on Mo(IV)-tetrakis(diethylaminodithiocarbomato). The surface chemistry of the MoS2 nanosheets has been studied in order to evaluate the chemical reactivities of the basal planes and edges. By irradiating the MoS2 nanosheet with a scanning infrared laser, micron-scale lithographical structures can be created due to laser-induced oxidation of MoS2 to form nanocrystalline MoO3. Preferential reactivities of the MoS2 basal edges in an electrochemical environment and during vapor phase deposition have been demonstrated. Functionalization of the basal plane with 1-pyrene acetic acid allows the immobilization of DNA and immunoglobins on the MoS2 basal plane.
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