Methacryloyl end-functionalized block copolymers consisting of styrene and vinyl-2-pyridine were polymerized to poly(block co-macromonomer)s with a much higher main chain than side chain degree of polymerization. Like homo-polymacromonomers these molecules exhibit the structure of cylindrical brushes. Since the vinylpyridine block is coupled to the polymerizable group, the resulting cylindrical macromolecules exhibit a core of vinylpyridine and a shell of polystyrene, thus forming an amphipolar core-shell cylindrical macromolecule. The core-shell character of the molecules was demonstrated by HRTEM utilizing selective positive staining for the core and for the core and the shell. The core of the cylindrical brushes was loaded with HAuCl 4 in toluene or methylene chloride followed by reduction of the noble metal salt by the electron beam, by UV light, or by chemical reducing agents. Depending on the amount of complexed noble metal ions and the reduction conditions, either a linear array of noble metal cluster or a continuous nanowire is formed most probably within the core of the cylindrical brushes. The resulting metal nanowires are much longer than the individual core-shell macromolecules which is caused by a yet unexplained specific end-to-end aggregation of the cylindrical polymers upon loading with HAuCl 4.
A new biological approach to fabricate Au nanowires was examined by using sequenced histidine-rich peptide nanowires as templates. The sequenced histidine-rich peptide molecules were assembled as nanowires, and the biological recognition of the sequenced peptide toward Au lead to efficient Au coating on the nanowires. Monodisperse Au nanocrystals were uniformly coated on the histidine peptide nanowires with the high-density coverage, and the crystalline phases of the Au nanocrystals were observed as (111) and (220). The uniformity of the Au coating on the nanowires without contamination of precipitated Au aggregates is advantageous for the fabrication of electronics and sensor devices when the nanowires are used as the building blocks. We believe this simple metal nanowire fabrication method can be applied to various metals and semiconductors with peptides whose sequences are known to mineralize specific ions.
A new biological approach to fabricate Au nanowires was examined by using sequenced peptide nanotubes as templates. The sequenced histidine-rich peptide molecules were assembled on nanotubes, and the biological recognition of the sequenced peptide selectively trapped Au ions for the nucleation of Au nanocrystals. After Au ions were reduced, highly monodisperse Au nanocrystals were grown on nanotubes. The conformations and the charge distributions of the histidine-rich peptide, determined by pH and Au ion concentration in the growth solution, control the size and the packing density of Au nanocrystals. The diameter of Au nanocrystal was limited by the spacing between the neighboring histidine-rich peptides on nanotubes. A series of TEM images of Au nanocrystals on nanotubes in the shorter Au ion incubation time periods reveal that Au nanocrystals grow inside the nanotubes first and then cover the outer surfaces of nanotubes. Therefore, multiple materials will be coated inside and outside the nanotubes respectively by controlling doping ion concentrations and their deposition sequences. It should be noted that metallic nanocrystals in diameter around 6 nm are in the size domain to observe a significant conductivity change by changing the packing density, and therefore this system may be developed into a conductivity-tunable building block.
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