Comparative studies on adsorption behavior of thionine on gold nanoparticles with different sizes

The adsorption behavior of thionine on gold nanoparticles of two different mean diameters, 18 and 5 nm, was compared by using UV-vis spectroscopy, fluorescence spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), dynamic light scattering (DLS), and quantum chemical calculations. It is found that the addition of small particles makes the monomer peak of thionine finally disappear, and the corresponding dimer peak is significantly increased. Small gold nanoparticles make the equilibrium between the monomer and H-type dimer forms of thionine move largely toward the dimer forms. Due to the stronger binding between thionine and small gold nanoparticles, the fluorescence quenching of thionine by small particles is enhanced compared to large particles, and the quenching is both static and dynamic. TEM images indicate that the addition of thionine results in a heavy clustering for small particles, and the resulting thionine-gold nanoclusters of about 45 nm were obtained. Quantum chemical calculations, which were based on the density functional theory (DFT) at the B3LYP level, and infrared spectroscopic studies show that the nitrogen atoms of the NH(2) moieties of thionine bind to the gold nanoparticle surfaces. For 18 and 5 nm particles, the surface-to-volume atomic ratios are about 0.0597 and 0.2148, respectively. The higher surface-to-volume atomic ratio and the higher surface free energy result in stronger binding of thionine on small particle surfaces, which can be used to modulate the arrangement of dye molecules on particle surfaces, and thus control the properties of organic-inorganic nanocomposite materials.