Copper(II)-containing aluminum phosphate material (CuAPO-5) was synthesized hydrothermally and used as a multiphase catalyst for the oxidation of α-pinene to verbenone. The catalysts were analyzed using X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area techniques, X-ray photoelectron spectroscopy (XPS), and ammonia temperature programmed reduction (NH3-TPD). Scanning electron microscopy (SEM), X-ray energy spectrometry (EDS), inductively coupled plasma emission spectroscopy (ICP-OES), Fourier infrared spectroscopy (FT-IR), and ultraviolet-visible spectroscopy (UV-vis) were performed to characterize the material. The effects of reaction temperature, reaction time, n(α-pinene)/n(TBHP), and solvent on the catalytic performance of CuAPO-5 were investigated. The results show that all the prepared catalysts have AFI topology and a large specific surface area. Copper is evenly distributed in the skeleton in a bivalent form. The introduction of copper increases the acid content of the catalyst. Under the optimized reaction conditions, 96.8% conversion of α-pinene and 46.4% selectivity to verbenone were achieved by CuAPO-5(0.06) molecular sieve within a reaction time of 12 h. CuAPO-5(0.06) can be recycled for five cycles without losing the conversion of α-pinene and the selectivity to verbenone.Keywords:CuAPO-5;α-pinene;selective oxidation;verbenone
Bark beetles are the most important mortality agent in coniferous forests, and pheromones play important roles in their management. Dendroctonus valens LeConte was introduced from North America to China and has killed millions of healthy pines there. Trapping with semiochemicals and pheromones was deployed in D. valens management in the last decade, but little is known about the ability of gut bacteria to produce the pheromone. In this study, we analyzed the volatiles in D. valens guts and frass after antibiotic treatment versus control. Then, we isolated and identified the bacteria in D. valens guts and frass, examined verbenone (a multifunctional pheromone of D. valens ) production by 16 gut bacterial isolates from the precursor cis -verbenol at three concentrations, and further compared the cytotoxicities between the cis -verbenol and verbenone to the bacterial isolates. cis -Verbenol was not detected in the frass in the control group, but it was in the antibiotic treatment. The amount of verbenone was significantly suppressed in D. valens guts after antibiotic treatment versus control. Thirteen out of 16 gut bacterial isolates were capable of cis -verbenol to verbenone conversion, and cis -verbenol had stronger cytotoxicities than verbenone to all tested gut bacterial isolates. The bacterial species capable of verbenone production largely exists in D. valens guts and frass, suggesting that gut-associated bacteria may help the bark beetle produce the pheromone verbenone in guts and frass. The bacteria may benefit from the conversion due to the reduced cytotoxicity from the precursor to the beetle pheromone.
危险品化学品经营许可证（带存储）