Ultrafast photoinduced enhancement of nonlinear optical response in 15-atom gold clusters on indium tin oxide conducting film.

We show that the third order optical nonlinearity of 15-atom gold clusters is significantly enhanced when in contact with indium tin oxide (ITO) conducting film. Open and close aperture z-scan experiments together with non-degenerate pump-probe differential transmission experiments were done using 80 fs laser pulses centered at 395 nm and 790 nm on gold clusters encased inside cyclodextrin cavities. We show that two photon absorption coefficient is enhanced by an order of magnitude as compared to that when the clusters are on pristine glass plate. The enhancement for the nonlinear optical refraction coefficient is ~3 times. The photo-induced excited state absorption using pump-probe experiments at pump wavelength of 395 nm and probe at 790 nm also show an enhancement by an order of magnitude. These results attributed to the excited state energy transfer in the coupled gold cluster-ITO system are different from the enhancement seen so far in charge donor-acceptor complexes and nanoparticle-conjugate polymer composites.

Luminescent, freestanding composite films of Au15 for specific metal ion sensing.

A highly luminescent freestanding film composed of the quantum cluster, Au(15), was prepared. We studied the utility of the material for specific metal ion detection. The sensitivity of the red emission of the cluster in the composite to Cu(2+) has been used to make a freestanding metal ion sensor, similar to pH paper. The luminescence of the film was stable when exposed to several other metal ions such as Hg(2+), As(3+), and As(5+). The composite film exhibited visual sensitivity to Cu(2+) up to 1 ppm, which is below the permissible limit (1.3 ppm) in drinking water set by the U.S. environmental protection agency (EPA). The specificity of the film for Cu(2+) sensing may be due to the reduction of Cu(2+) to Cu(1+)/Cu(0) by the glutathione ligand or the Au(15) core. Extended stability of the luminescence of the film makes it useful for practical applications.

Functionalized Au22 clusters: synthesis, characterization, and patterning.

We synthesized fluorescent, porphyrin-anchored, Au(22) clusters in a single step, starting from well-characterized Au(25) clusters protected with glutathione (-SG) by a combined core reduction/ligand exchange protocol, at a liquid-liquid interface. The prepared cluster was characterized by UV/vis, photoluminescence, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, elemental analysis, and matrix-assisted laser desorption ionization mass spectrometry. The absence of a 672 nm intraband transition of Au(25) and the simultaneous emergence of new characteristic peaks at 520 and 635 nm indicate the formation of the Au(22) core. An increase in the binding energy of 0.4 eV in Au 4f core-level peaks confirmed the presence of a reduced core size. Quantitative XPS confirmed the Au/S ratio. The presence of a free base, tetraphenylporphyrin (H(2)TPPOAS-), on the Au(22) core was confirmed by fluorimetric titrations with Cu(2+) and Zn(2+) ions. From all of these, the composition of the cluster was determined to be Au(22)[(-SG)(15)(-SAOPPTH(2))(2)], which was supported by mass spectrometry and elemental analysis. We utilized the fluorescence nature of these water-soluble clusters for the fabrication of fluorescent patterns by soft lithography. The patterns were studied using tapping-mode atomic force microscopy and confocal fluorescence imaging.