Two-dimensional gold nanostructures have been fabricated by electrochemical deposition of gold nanoparticles onto indium tin oxide (ITO) glass substrate modified with thin polypyrrole film. By controlling the electrodeposition conditions, gold nanoparticles with dendritic rod, sheet, flower-like (consisting of staggered nanosheets), and pinecone-like structures were generated. The flower-like gold nanoparticles showed high catalytic activity on electrochemical reduction of oxygen, and its activity was measured to be approximately 25 times that of gold pinecones and 10(4) times that of gold nanosheets in terms of gold weight. The pinecone-like nanoparticles can form a compact film with nano-/microscale binary structure like a lotus leaf surface. After modification with n-dodecanethiol, the surface showed superhydrophobic properties with a water contact angle of 153.4 degrees and a tilt angle of 4.4 degrees (5 microL droplet).
Molybdate-based inorganic-organic hybrid disks with a highly ordered layered structure were synthesized via an acid-base reaction of white molybdic acid (MoO 3 $H 2 O) with n-octylamine (C 8 H 17 NH 2 ) in ethanol at room temperature. The thermal treatment of the as-obtained molybdatebased inorganic-organic hybrid disks at 550 C in air led to formation of orthorhombic a-MoO 3 nanoplates. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal analysis (TG-DTA), Fourier-transform infrared (FT-IR) spectra, Raman spectra, and a laser-diffraction grain-size analyzer were used to characterize the starting materials, the intermediate hybrid precursors and the final a-MoO 3 nanoplates. The XRD, FT-IR and TG-DTA results suggested that the molybdate-based inorganic-organic hybrid compound, with a possible composition of (C 8 H 17 NH 3 ) 2 MoO 4 , was of a highly ordered lamellar structure with an interlayer distance of 2.306(1) nm, and the n-alkyl chains in the interlayer places took a double-layer arrangement with a tilt angle of 51 against the inorganic MoO 6 octahedra layers. The SEM images indicated that the molybdate-based inorganic-organic hybrids took on a well-dispersed disk-like morphology, which differed distinctly from the severely aggregated morphology of their starting MoO 3 $H 2 O powders. During the calcining process, the disk-like morphology of the hybrid compounds was well inherited into the orthorhombic a-MoO 3 nanocrystals, showing a definite plate-like shape. The a-MoO 3 nanoplates obtained were of a single-crystalline structure, with a side-length of 1-2 mm and a thickness of several nanometres, along a thickness direction of [010]. The above a-MoO 3 nanoplates were of a loose aggregating texture and high dispersibility. The chemical sensors derived from the as-obtained a-MoO 3 nanoplates showed an enhanced and selective gas-sensing performance towards ethanol vapors. The a-MoO 3 nanoplate sensors reached a high sensitivity of 44-58 for an 800 ppm ethanol vapor operating at 260-400 C, and their response times were less than 15 s.
Rational utilization of nanomaterials to construct electrochemical nucleic acid sensors has attracted large attention in recent years. In this work, we systematically interrogate the interaction between gold nanoparticles (GNPs) and single-strand DNA (ssDNA) immobilized on an electrode surface and then take advantage of the ultrahigh charge-transfer efficiency of GNPs to develop a novel DNA sensing method. Specifically, ssDNA modified gold electrode can adsorb GNPs because of the interaction between gold and nitrogen-containing bases; thus, the negative electrochemical species [Fe(CN)6](3-/4-) may transfer electrons to electrode through adsorbed GNPs. In the presence of target DNA, the formed double-strand DNA (dsDNA) cannot capture GNPs onto the electrode surface and the dsDNA may result in a large charge-transfer resistance owing to the negatively charged phosphate backbones of DNA. So a simple but sensitive method for the detection of target DNA can be developed by using GNPs without any requirement of modification. Experimental results demonstrate that the electrochemical method we have proposed in this work can detect as low as 1 pM breast cancer gene BRCA1 in a 10 μL sample volume without any signal amplification process or the involvement of other synthesized complex, which may provide an alternative for cancer DNA detection. This method may also be generalized for detecting a spectrum of targets using functional DNA (aptamer, metal-specific oligonucleotide, or DNAzyme) in the future.
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