Mechanism of formation of supramolecular DNA-templated polymer nanowires.
Details of the mechanism of formation of supramolecular polymer nanowires by templating on DNA are revealed for the first time using AFM. Overall these data reveal that the smooth, regular, structures produced are rendered by highly dynamic supramolecular transformations occurring over the micrometre scale. In the initial stages of the process a low density of conducting polymer (CP) binds to the DNA as, essentially, spherical particles. Further reaction time produces DNA strands which are more densely packed with particles giving a beads-on-a-string appearance. The particles subsequently undergo dynamic reconfiguration so as to elongate along the template axis and merge to yield the highly regular, smooth morphology of the final nanowire. MD simulations illustrate the early stages of the process showing the binding of globular CP to duplex DNA, while the latter stages can be modeled effectively by a linear thermodynamic description based on the balance between the line energy, which accounts for adhesion of the material to the template, and its surface tension. This model accounts for the phenomena observed in the AFM studies: the relative success of DNA templating of polymers compared to metals; the slow approach to equilibrium; and the observed thinning and 'necking' phenomena as the structures transform from beads-on-a-string to smooth nanowire.
Chemical Nanoscience Laboratories, School of Chemistry, Newcastle University , Bedson Building, Newcastle upon Tyne, NE1 7RU United Kingdom.
Scott M D
SM
Watson
Miguel A
MA
Galindo
Benjamin R
BR
Horrocks
Andrew
A
Houlton
D004247:DNA / Q000737:chemistry*; D053770:Nanowires; D011108:Polymers / Q000737:chemistry*; D013816:Thermodynamics
D011108:Polymers; D004247:DNA