Lead immobilization in mechanochemical fly ash recycling

In previous studies, we focused on a mechanochemical process for recycling fly ash for use in cement; this process was expected to immobilize heavy metals in the fly ash, a desirable outcome in light of the fact that recycled fly ash is commonly used in the synthesis of inorganic materials. Here, we investigated the leaching of lead (Pb) from fly ash treated by a mechanochemical process and from cement prepared from the treated fly ash. We used lead oxide (PbO), a typical Pb compound in fly ash, as a model substance. Mechanochemical treatment of the fly ash inhibited Pb leaching by 93%, and further inhibition (more than 99.9%) was observed in cement produced from the treated fly ash. During the mechanochemical treatment, PbO was reduced to Pb by iron from the stainless-steel mill used for processing, and the lower solubility of Pb in water resulted in immobilization of the Pb.     

Pyrolysis of tetrabromobisphenol-A containing paper laminated printed circuit boards

Tetrabromobisphenol-A (TBBA) is the most common brominated fire retardant. In this study, a TBBA containing paper laminated printed circuit board (PCB) prepared from novolac was pyrolysed by both TGA and in a quartz glass reactor between 40 and 1,000 degrees C. The products were online detected by MS. It was found that the PCB degraded in three steps. Step one (<270 degrees C) consisted of the evolution of water and CO(2) from the paper laminate. In the second step, between 270 and 370 degrees C, the fire retardant decomposed, releasing HBr and brominated aromatics. In the third step, at temperatures above 370 degrees C, the phenol resin decomposed and char was formed. Compared to pure TBBA, which mainly produces brominated phenols, the brominated products enclosed in the char released HBr during the last degradation step as well as during the second step. Most of the bromine left the resin in the form of HBr, with about 14% of the bromine being fixed in brominated aromatics and less than 2% remaining in the residue.     

A new class of mealybug pheromones: a hemiterpene ester in the sex pheromone of Crisicoccus matsumotoi

Mealybugs, which include several agricultural pests, are small sap feeders covered with a powdery wax. They exhibit clear sexual dimorphism; males are winged but fragile and short lived, whereas females are windless and less mobile. Thus, sex pheromones emitted by females facilitate copulation and reproduction by serving as a key navigation tool for males. Although the structures of the hitherto known mealybug pheromones vary among species, they have a common structural motif; they are carboxylic esters of monoterpene alcohols with irregular non-head-to-tail linkages. However, in the present study, we isolated from the Matsumoto mealybug, Crisicoccus matsumotoi (Siraiwa), a pheromone with a completely different structure. Using gas chromatography–mass spectrometry and nuclear magnetic resonance spectroscopy, we identified the pheromone as 3-methyl-3-butenyl 5-methylhexanoate. Its attractiveness to males was confirmed in a series of field trapping experiments involving comparison between the isolated natural product and a synthetic sample. This is the first report of a hemiterpene mealybug pheromone. In addition, the acid moiety (5-methylhexanoate) appears to be rare in insect pheromones.     

A convenient and eco-friendly way to synthesize Pt(II) and Pd(II) porphyrins in ionic liquids by microwave activation

Due to the slow rate of incorporation of inert-metal ions into free-base porphyrins compared to other transition metals, several methods have been proposed to accelerate the rate of metalation. However, these methods have disadvantages such as low yields, difficulties of purification of final products, and environmental effects. To avoid those disadvantages, we reacted Pt(II) and Pd(II) salts with H₂(TPP), H₂(TMPyP)⁴⁺, and their β-pyrrole derivatives, H₂(Br₈TPP) and H₂(Br₈TMPyP)⁴⁺, in 1-butyl-3-methylimidazolium bromide ([bmim]⁺Br⁻) under microwave irradiation. The combination of microwave heating and ionic liquids provides efficient thermal energy transfer among the porphyrins and metal salts. In addition, ionic liquids stabilize charged species as well as their intermediates, due to their high dipole moment and high boiling point. This not only shortens the reaction time but also gives high yields of products at relatively low temperatures, of about 100°C compared to conventional synthesis methods: 150°C for DMF, 190°C for DMSO. Here, we demonstrate that Pt(II)/Pt(II) metalloporphyrins are synthesized at high rates, e.g. 6–30 min for 100% metalation, with high yields of 79–93% in [bmim]⁺Br⁻ by microwave activation.