Chemical, Structural, and Morphological Changes of a MoVTeNb Catalyst during Oxidative Dehydrogenation of Ethane

MoVTeNb mixed oxide, a highly active and selective catalyst for the oxidative dehydrogenation of ethane to produce ethylene, exhibits the so-called M1 and M2 crystalline phases. The thermal stability of the MoVTeNb catalytic system was assessed under varying reaction conditions; to this end, the catalyst was exposed to several reaction temperatures spanning from 440 to 550 °C. Both the pristine and spent materials were analyzed by several characterization techniques. The catalyst was stable below 500 °C; a reaction temperature of ≥500 °C brings about the removal of tellurium from the intercalated framework channels of the M1 crystalline phase. Rietveld refinement of X-ray diffraction patterns and microscopy results showed that the tellurium loss causes the progressive partial destruction of the M1 phase, thus decreasing the number of active sites and forming a MoO2 crystalline phase, which is inactive for this reaction. Raman spectroscopy confirmed the MoO2 phase development as a function of reaction temperature. From highresolution transmission electron microscopy and energy-dispersive X-ray spectroscopy analyses it was noticed that tellurium departure occurs preferentially from the end sides of the needlelike M1 crystals, across the [001] plane. Detailed analysis of a solid deposited at the reactor outlet showrf that it consisted mainly of metallic tellurium, suggesting that the tellurium detachment occurs via reduction of Te4+ to Te0 due to a combination of reaction temperature and feed composition. Thus, in order to sustain the catalytic performance exhibited by MoVTeNb mixed oxide, hot spots along the reactor bed should be avoided or controlled, maintaining the catalytic bed temperature below 500 °C.This work was financially supported by the Instituto Mexicano del Petroleo.Valente, JS.; Armendariz-Herrera, H.; Quintana-Solorzano, R.; Del Angel, P.; Nava, N.; Masso Ramírez, A.; López Nieto, JM. (2014). Chemical, Structural, and Morphological Changes of a MoVTeNb Catalyst during Oxidative Dehydrogenation of Ethane. ACS Catalysis. 4:1292-1301. doi:10.1021/cs500143jS12921301

Transcriptional responses underlying the hormetic and detrimental effects of the plant secondary metabolite gossypol on the generalist herbivore Helicoverpa armigera

<p>Abstract</p> <p>Background</p> <p>Hormesis is a biphasic biological response characterized by the stimulatory effect at relatively low amounts of chemical compounds which are otherwise detrimental at higher concentrations. A hormetic response in larval growth rates has been observed in cotton-feeding insects in response to increasing concentrations of gossypol, a toxic metabolite found in the pigment glands of some plants in the family Malvaceae. We investigated the developmental effect of gossypol in the cotton bollworm, <it>Helicoverpa armigera</it>, an important heliothine pest species, by exposing larvae to different doses of this metabolite in their diet. In addition, we sought to determine the underlying transcriptional responses to different gossypol doses.</p> <p>Results</p> <p>Larval weight gain, pupal weight and larval development time were measured in feeding experiments and a hormetic response was seen for the first two characters. On the basis of net larval weight gain responses to gossypol, three concentrations (0%, 0.016% and 0.16%) were selected for transcript profiling in the gut and the rest of the body in a two-color double reference design microarray experiment. Hormesis could be observed at the transcript level, since at the low gossypol dose, genes involved in energy acquisition such as β-fructofuranosidases were up-regulated in the gut, and genes involved in cell adhesion were down-regulated in the body. Genes with products predicted to be integral to the membrane or associated with the proteasome core complex were significantly affected by the detrimental dose treatment in the body. Oxidoreductase activity-related genes were observed to be significantly altered in both tissues at the highest gossypol dose.</p> <p>Conclusions</p> <p>This study represents the first transcriptional profiling approach investigating the effects of different concentrations of gossypol in a lepidopteran species. <it>H. armigera</it>'s transcriptional response to gossypol feeding is tissue- and dose-dependent and involves diverse detoxifying mechanisms not only to alleviate direct effects of gossypol but also indirect damage such as pH disturbance and oxygen radical formation. Genes discovered through this transcriptional approach may be additional candidates for understanding gossypol detoxification and coping with gossypol-induced stress. In a generalist herbivore that has evolved transcriptionally-regulated responses to a variety of different plant compounds, hormesis may be due to a lower induction threshold of growth-promoting, stress-coping responses and a higher induction threshold of detoxification pathways that are costly and cause collateral damage to the cell.</p