New Hybrid Properties of TiO2 Nanoparticles Surface Modified With Catecholate Type Ligands

Surface modification of nanocrystalline TiO2 particles (45 Å) with bidentate benzene derivatives (catechol, pyrogallol, and gallic acid) was found to alter optical properties of nanoparticles. The formation of the inner-sphere charge–transfer complexes results in a red shift of the semiconductor absorption compared to unmodified nanocrystallites. The binding structures were investigated by using FTIR spectroscopy. The investigated ligands have the optimal geometry for chelating surface Ti atoms, resulting in ring coordination complexes (catecholate type of binuclear bidentate binding–bridging) thus restoring in six-coordinated octahedral geometry of surface Ti atoms. From the Benesi–Hildebrand plot, the stability constants at pH 2 of the order 103 M−1 have been determined

Photoluminescence Stokes shift and exciton fine structure in CdTe nanocrystals

The photoluminescence spectra of spherical CdTe nanocrystals with zincblende structure are studied by size-selective spectroscopic techniques. We observe a resonant Stokes shift of 15 meV when the excitation laser energy is tuned to the red side of the absorption band at 2.236 eV. The experimental data are analyzed within a symmetry-based tight-binding theory of the exciton spectrum, which is first shown to account for the size dependence of the fundamental gap reported previously in the literature. The theoretical Stokes shift presented as a function of the gap shows a good agreement with the experimental data, indicating that the measured Stokes shift indeed arises from the electron-hole exchange interaction.Comment: 8 pages, 4 figures, LaTe

Combined photooxidation/photoreduction using TiO{sub 2} photocatalysts to treat organic/inorganic metal-laden wastewaters

Titanium dioxide (TiO{sub 2}) colloids prepared from titanium chloride (TiCl{sub 4}) were used as photocatalysts in the experiments. Cysteine was selected as the model derivative for the surface modification of the TiO{sub 2} nanoparticles. Testing of TiO{sub 2} photocatalysts conducted in the absence of organic compounds demonstrated that adsorption of lead ions occurred in the system with either untreated (virgin) or treated (modified using cysteine) TiO{sub 2} photocatalysts. Adsorption rates of the metal ions in the systems that used treated TiO{sub 2} photocatalysts were about three times faster than those where untreated TiO{sub 2} photocatalysts were used. Lead ion concentrations in the irradiated solutions decreased as the UV irradiation time increased; greater metal removals were achieved at longer irradiation times. The rate of decreasing lead ion concentrations in the system that used treated TiO{sub 2} photocatalysts was about two to three times faster than that in the system using untreated TiO{sub 2} photocatalysts. Experiments were also performed in which organic compounds (naphthalene or phenol) and heavy metals (Pb{sup 2+}) were simultaneously treated with TiO{sub 2} photocatalysts. The presence of lead ions did not interfere with the photo-degradation of the selected organic compounds from solution. The presence of phenol compound appeared not to affect the photoreduction of lead ions, while addition of naphthalene compound resulted in a lag-time effect on the photoreduction of lead ions from solution. All of the experimental results showed that the cysteine-modified TiO{sub 2} resulted in faster and more effective removal than that for the untreated TiO{sub 2} system. This technique has resulted in the simultaneous photocatalytic removal/recovery of organic and inorganic compounds in the system

Intracellular localization of titanium dioxide-biomolecule nanocomposites.

Emerging areas of nanotechnology hold the promise of overcoming the limitations of existing technology for intracellular manipulation. These new developments include the creation of nanocomposites that can be introduced into the cells, targeted to specific subcellular sites, and subsequently used as platforms for initiation of intracellular processes dependent on or aided by locally high concentrations of specific molecules delivered as components of the nanocomposites. Nanocomposites that combine functional properties of biomolecules with the functional properties of inorganic components could provide new tools for biology, medicine, chemistry and material sciences. Here we describe how we introduced TiO{sub 2}-DNA nanocomposites into cells, and localized titanium in the cells by mapping the Ti K{alpha} X-ray fluorescence induced at the 2-ID-E microprobe of the SRI-CAT at the Advanced Photon Source at Argonne National Laboratory

Nanoparticles for Applications in Cellular Imaging

In the following review we discuss several types of nanoparticles (such as TiO2, quantum dots, and gold nanoparticles) and their impact on the ability to image biological components in fixed cells. The review also discusses factors influencing nanoparticle imaging and uptake in live cells in vitro. Due to their unique size-dependent properties nanoparticles offer numerous advantages over traditional dyes and proteins. For example, the photostability, narrow emission peak, and ability to rationally modify both the size and surface chemistry of Quantum Dots allow for simultaneous analyses of multiple targets within the same cell. On the other hand, the surface characteristics of nanometer sized TiO2allow efficient conjugation to nucleic acids which enables their retention in specific subcellular compartments. We discuss cellular uptake mechanisms for the internalization of nanoparticles and studies showing the influence of nanoparticle size and charge and the cell type targeted on nanoparticle uptake. The predominant nanoparticle uptake mechanisms include clathrin-dependent mechanisms, macropinocytosis, and phagocytosis