Raman scattering of molecules adsorbed on the surface of TiO(2) nanoparticles was investigated. We find strong enhancement of Raman scattering in hybrid composites that exhibit charge transfer absorption with TiO(2) nanoparticles. An enhancement factor up to approximately 10(3) was observed in the solutions containing TiO(2) nanoparticles and biomolecules, including the important class of neurotransmitters such as dopamine and dopac (3,4-dihydroxy-phenylacetic acid). Only selected vibrations are enhanced, indicating molecular specificity due to distinct binding and orientation of the biomolecules coupled to the TiO(2) surface. All enhanced modes are associated with the asymmetric vibrations of attached molecules that lower the symmetry of the charge transfer complex. The intensity and the energy of selected vibrations are dependent on the size and shape of nanoparticle support. Moreover, we show that localization of the charge in quantized nanoparticles (2 nm), demonstrated as the blue shift of particle absorption, diminishes SERS enhancement. Importantly, the smallest concentration of adsorbed molecules shows the largest Raman enhancements suggesting the possibility for high sensitivity of this system in the detection of biomolecules that form a charge transfer complex with metal oxide nanoparticles. The wavelength-dependent properties of a hybrid composite suggest a Raman resonant state. Adsorbed molecules that do not show a charge transfer complex show weak enhancements probably due to the dielectric cavity effect.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and (•)OH radicals (oxidation product) from water, and CO(3)(-) radical anions (oxidation product) from carbonates, was detected in CO(2)-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, (•)OCH(3), and methyl, (•)CH(3), radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO(2) on the surface of TiO(2) is supported by the results of first-principles calculations.

Coupled CuO−TiO2 nanocomposite photocatalysts were prepared by a deposition precipitation method and were characterized with a variety of techniques. Electron paramagnetic resonance (EPR) spectroscopy was employed to study the local structures of surface/interfacial Cu2+ sites using Cu2+ as a sensitive paramagnetic probe. The addition of bulk CuO to TiO2 led to decreased photocatalytic efficiency in the degradation of methylene blue. However, doping with a very small amount of CuO (0.1 wt % copper loading) significantly enhanced the photocatalytic activity of TiO2. EPR study of the TiO2 surface revealed the presence of both highly dispersed CuO clusters and substitutional Cu2+ sites (Ti−O−Cu linkages) at 0.1 wt % copper loading. The data suggest that the Ti−O−Cu linkages contributed to the improved photooxidative activity of the 0.1% CuO−TiO2 nanocomposite. In contrast, at higher loadings the bulk form of CuO created charge recombination centers lowering the photoactivity of the composites.

Semiconductor quantum dots (QDs) have been widely used for fluorescent labelling. However, their ability to transfer electrons and holes to biomolecules leads to spectral changes and effects on living systems that have yet to be exploited. Here we report the first cell-based biosensor based on electron transfer between a small molecule (the neurotransmitter dopamine) and CdSe/ZnS QDs. QD-dopamine conjugates label living cells in a redox-sensitive pattern: under reducing conditions, fluorescence is only seen in the cell periphery and lysosomes. As the cell becomes more oxidizing, QD labelling appears in the perinuclear region, including in or on mitochondria. With the most-oxidizing cellular conditions, QD labelling throughout the cell is seen. Phototoxicity results from the creation of singlet oxygen, and can be reduced with antioxidants. This work suggests methods for the creation of phototoxic drugs and for redox-specific fluorescent labelling that are generalizable to any QD conjugated to an electron donor.