Crystallization of metallic nanoparticles on short DNA oligonucleotides in alkaline aqueous solution

Silver, zinc, and copper nanoparticles were reductively crystallized on thymine-containing single-stranded DNA decanucleotides, in aqueous solutions containing the corresponding metal ions and sodium borohydride, at 4 °C, pH 11.8, and 15 mM of NaCl. Iron nanoparticles were not formed under these conditions. Formation of aggregates was monitored by UV-Vis spectrophotometry, and characterized by scanning electron microscopy and dynamic light scattering. The absorption spectra for most Ag+-containing samples showed a major band centered around 425 nm and a shoulder between 500 and 600 nm, indicative of the presence of silver particles in a wide size distribution, in the 0.1–5 μm range. This was verified by micrographs and size distribution observed in scattering profiles. Silver-particle morphology indicates formation of cubic structures instead of spherical geometries. For the case of zinc and copper nanoparticles, quasi-spherical structures of approximately 100 nm were crystallized along the DNA chains by reduction reaction, and then released to the bulk solvent. Thymine residues show a higher effectiveness in nucleation of metallic cations in comparison to other DNA nucleobases, particularly in their deprotonated form, at high pH values. Adenines flanking central runs of deprotonable bases in the model oligonucletide chain affect the production of silver crystals on the DNA decamers. pH value and NaCl concentration have a significant effect on the production of silver particles, as alkaline and moderate-ionic-strength conditions are required to crystallize such structures. The tuning of size and morphology of metallic nanoparticles by the proper choice of oligonucleotide sequence and physical conditions may have interesting applications in the field of nanobiotechnology.