Double and triple lanthanide ion (Ln(3+))-doped synthetic double crossover (DX) DNA lattices and natural salmon DNA (SDNA) thin films are fabricated by the substrate assisted growth and drop-casting methods on given substrates. We employed three combinations of double Ln(3+)-dopant pairs (Tb(3+)-Tm(3+), Tb(3+)-Eu(3+), and Tm(3+)-Eu(3+)) and a triple Ln(3+)-dopant pair (Tb(3+)-Tm(3+)-Eu(3+)) with different types of Ln(3+), (i.e., Tb(3+) chosen for green emission, Tm(3+) for blue, and Eu(3+) for red), as well as various concentrations of Ln(3+) for enhancement of specific functionalities. We estimate the optimum concentration of Ln(3+) ([Ln(3+)]O) wherein the phase transition of Ln(3+)-doped DX DNA lattices occurs from crystalline to amorphous. The phase change of DX DNA lattices at [Ln(3+)]O and a phase diagram controlled by combinations of [Ln(3+)] were verified by atomic force microscope measurement. We also developed a theoretical method to obtain a phase diagram by identifying a simple relationship between [Ln(3+)] and [Ln(3+)]O that in practice was found to be in agreement with experimental results. Finally, we address significance of physical characteristics-current for evaluating [Ln(3+)]O, absorption for understanding the modes of Ln(3+) binding, and photoluminescence for studying energy transfer mechanisms-of double and triple Ln(3+)-doped SDNA thin films. Current and photoluminescence in the visible region increased as the varying [Ln(3+)] increased up to a certain [Ln(3+)]O, then decreased with further increases in [Ln(3+)]. In contrast, the absorbance peak intensity at 260 nm showed the opposite trend, as compared with current and photoluminescence behaviors as a function of varying [Ln(3+)]. A DNA thin film with varying combinations of [Ln(3+)] might provide immense potential for the development of efficient devices or sensors with increasingly complex functionality.
Keywords: Co-doping; DNA lattice; DNA thin film; lanthanide ion; photoluminescence.