ABSTRACT
TiO2 particles with a specific morphology are essential for their accessibility and photoactivity. The present study shows that NH4OH-based alkaline-hydrothermal treatment affects the transformation of their particle morphology. We investigated the effect of NH4OH by varying the synthesis route. We observed that the TiO2 particles with an open channel pore structure only resulted in the alkaline-hydrothermally treated and calcined samples. Based on Raman and XRD analyses, we figured out the titanate layers as an intermediate phase resulting from the alkaline-hydrothermal treatment of the amorphous particles. The hydrothermal treatment changed the particle surface morphology into a lamellar structure with a high specific surface area. These are the anatase precursors with {200} planes that transform into the anatase phase after calcination. The calcination followed by alkaline-hydrothermal treatment converted the crystallinity without significantly changing their morphology. We found that the morphology of TiO2 particles can be modified via hydrothermal treatment using NH4OH as long as the particles remain uncrystallized. We suggested the modification of particle morphology through the swelling and phase segregation process by alkaline-hydrothermal treatment. All final products have been used for the photodegradation of rhodamine B. S-HT-500 and A-HT-500 show the best photocatalytic activity with their rate constants (k) of 47.9 and 30.9 × 10-2 min-1, and their surface area-normalized rate constants (ksa) of 6.5 and 2.6 × 10-3 L m-2 min-1, respectively, and have a photocatalytic efficiency of 90.93% and 67.78%, respectively, after 10 minutes of UV irradiation. This activity is approximately 3.5 times and 1.5 times higher than that of Degussa P25; 30 times and 20 times higher than that without a photocatalyst.
ABSTRACT
Chromium(III) nutritional supplements are widely used due to their purported ability to enhance glucose metabolism, despite growing evidence on low activity and the potential genotoxicity of these compounds. Reactivities of Cr(III) complexes used in nutritional formulations, including [Cr3O(OCOEt)6(OH2)3](+) (A), [Cr(pic)3] (pic=2-pyridinecarboxylato(-) (B), and trans-[CrCl2(OH2)4](+) (CrCl3.6H2O; C), in a range of natural and simulated biological media (artificial digestion systems, blood and its components, cell culture media, and intact L6 rat skeletal muscle cells) were studied by X-ray absorption near-edge structure (XANES) spectroscopy. The XANES spectroscopic data were processed by multiple linear-regression analyses with the use of a library of model Cr(III) compounds, and the results were corroborated by the results of X-ray absorption fine structure spectroscopy and electrospray mass spectrometry. Complexes A and B underwent extensive ligand-exchange reactions under conditions of combined gastric and intestinal digestion (in the presence of a semisynthetic meal, 3 h at 310 K), as well as in blood serum and in a cell culture medium (1-24 h at 310 K), with the formation of Cr(III) complexes with hydroxo and amino acid/protein ligands. Reactions of compounds A-C with cultured muscle cells led to similar ligand-exchange products, with at least part of Cr(III) bound to the surface of the cells. The reactions of B with serum greatly enhanced its propensity to be converted to Cr(VI) by biological oxidants (H2O2 or glucose oxidase system), which is proposed to be a major cause of both the insulin-enhancing activity and toxicity of Cr(III) compounds (Mulyani, I.; Levina, A.; Lay, P. A. Angew. Chem. Int. Ed. 2004, 43, 4504-4507). This finding enhances the current concern over the safety of consumption of large doses of Cr(III) supplements, particularly [Cr(pic)3].
Subject(s)
Chromium/chemistry , Dietary Supplements/analysis , Absorption , Buffers , Kinetics , Molecular Structure , Oxidation-Reduction , Spectrophotometry , X-RaysABSTRACT
Chromium(VI) is a human carcinogen, primarily affecting the respiratory tract probably via active transport into cells, followed by the reduction to Cr(III) with the formation of DNA-damaging intermediates. Distribution of Cr and endogenous elements within A549 human lung adenocarcinoma epithelial cells, following treatment with Cr(VI) (100 microM, 20 min or 4 h) were studied by synchrotron-radiation-induced X-ray emission (SRIXE) of single freeze-dried cells. After the 20-min treatment, Cr was confined to a small area of the cytoplasm and strongly co-localized with S, Cl, K, and Ca. After the 4-h treatment, Cr was distributed throughout the cell, with higher concentrations in the nucleus and the cytoplasmic membrane. This time-dependence corresponded to approximately 100% or 0% clonogenic survival of the cells following the 20-min or 4-h treatments, respectively, and could potentially be explained by a new cellular protective mechanism. Such processes may also be important in reducing the potential hazards of Cr(III) dietary supplements, for which there is emerging evidence that they exert their anti-diabetic effects via biological oxidation to Cr(VI). The predominance of Cr(III) was confirmed by micro-XANES spectroscopy of intracellular Cr hotspots. X-ray absorption spectroscopy (XANES and EXAFS, using freeze-dried cells after the 0-4-h treatments) was used to gain insight into the chemical structures of Cr(III) complexes formed during the intracellular reduction of Cr(VI). The polynuclear nature of such complexes (probably with a combination of carboxylato and hydroxo bridging groups and O-donor atoms of small peptides or proteins) was established by XAFS data analyses.
