Mechanochemical Vicinal Dibromination of Unactivated Alkenes and Alkynes Using Piezoelectric Material as a Redox Catalyst.

Mechanoredox chemistry is a rapidly evolving field at the intersection of mechanical forces and chemical reactions. Herein, we have reported a vicinal dibromination of unsaturated hydrocarbons using piezoelectric material (Li2TiO3) as a redox catalyst. Furthermore, the reaction can be efficiently scaled up to 10 mmol and performed under an air atmosphere at room temperature without solvents or external reductants, and Li2TiO3 can be reused multiple times without a structural change.

Fabrication and characterization of dense zirconia and zirconia-silica ceramic nanofibers.

The objective of this study was to prepare dense zirconia-yttria (ZY), zirconia-silica (ZS) and zirconia-yttria-silica (ZYS) nanofibers as reinforcing elements for dental composites. Zirconium (IV) propoxide, yttrium nitrate hexahydrate, and tetraethyl orthosilicate (TEOS) were used as precursors for the preparation of zirconia, yttria, and silica sols. A small amount (1-1.5 wt%) of polyethylene oxide (PEO) was used as a carry polymer. The sols were preheated at 70 degrees C before electrospinning and their viscosity was measured with a viscometer at different heating time. The gel point was determined by viscosity-time (eta-t) curve. The ZY, ZS and ZYS gel nanofibers were prepared using a special reactive electrospinning device under the conditions near the gel point. The as-prepared gel nanofibers had diameters between 200 and 400 nm. Dense (nonporous) ceramic nanofibers of zirconia-yttria (96/4), zirconia-silica (80/20) and zirconia-yttria-silica (76.8/3.2/20) with diameter of 100-300 nm were obtained by subsequent calcinations at different temperatures. The gel and ceramic nanofibers obtained were characterized by scanning electron microscope (SEM), high-resolution field-emission scanning electron microscope (FE-SEM), thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), Fourier transform infrared spectrometer (FT-IR), and X-ray diffraction (XRD). SEM micrograph revealed that ceramic ZY nanofibers had grained structure, while ceramic ZS and ZYS nanofibers had smooth surfaces, both showing no visible porosity under FE-SEM. Complete removal of the polymer PEO was confirmed by TGA/DSC and FT-IR. The formation of tetragonal phase of zirconia and amorphous silica was proved by XRD. In conclusion, dense zirconia-based ceramic nanofibers can be fabricated using the new reactive sol-gel electrospinning technology with minimum organic polymer additives.

Synthesis of TiO2 photocatalysts in supercritical CO2 via a non-hydrolytic route.

Nanoscaled TiO2 powders with narrow size dispersion were prepared in supercritical carbon dioxide via non-hydrolytic acylation/deacylation of titanium alkoxide precursors with or without tris-fluorination. The microstructures of these powders were characterized by spectroscopic (FTIR, TGA, and XRD), microscopic (SEM or TEM), and surface area (BET) measurements. Photocatalytic oxidation of 1-octanol on these calcined TiO2 powders and on commercial T805 TiO2 suspended in aerated supercritical carbon dioxide revealed relative reactivity controlled by the powder microstructures. Calcined TiO2 prepared from titanium(IV) isopropoxide and trifluoroacetic anhydride was effectively dispersed in aerated supercritical carbon dioxide under stirring and exhibited high photocatalytic oxidation activity.

Novel dental composites reinforced with zirconia-silica ceramic nanofibers.

OBJECTIVE: To fabricate and characterize dental composites reinforced with various amounts of zirconia-silica (ZS) or zirconia-yttria-silica (ZYS) ceramic nanofibers. METHODS: Control composites (70 wt% glass particle filler, no nanofibers) and experimental composites (2.5, 5.0, and 7.5 wt% ZS or ZYS nanofibers replacing glass particle filler) were prepared by blending 29 wt% dental resin monomers, 70 wt% filler, and 1.0 wt% initiator, and polymerized by either heat or dental curing light. Flexural strength (FS), flexural modulus (FM), energy at break (EAB), and fracture toughness (FT) were tested after the specimens were stored in 37°C deionized water for 24h, 3 months, or 6 months. Degree of conversion (DC) of monomers in composites was measured using Fourier transformed near-infrared (FT-NIR) spectroscopy. Fractured surfaces were observed by field-emission scanning electron microscope (FE-SEM). The data were analyzed using ANOVA with Tukey's Honestly Significant Differences test used for post hoc analysis. RESULTS: Reinforcement of dental composites with ZS or ZYS nanofibers (2.5% or 5.0%) can significantly increase the FS, FM and EAB of dental composites over the control. Further increase the content of ZS nanofiber (7.5%), however, decreases these properties (although they are still higher than those of the control). Addition of nanofibers did not decrease the long-term mechanical properties of these composites. All ZS reinforced composites (containing 2.5%, 5.0% and 7.5% ZS nanofibers) exhibit significantly higher fracture toughness than the control. The DC of the composites decreases with ZS nanofiber content. SIGNIFICANCE: Incorporation of ceramic nanofibers in dental composites can significantly improve their mechanical properties and fracture toughness and thus may extend their service life.