Environmentally friendly, heterogeneous acid and base catalysis for the methylation of catechol: Chances for the control of chemo-selectivity

The properties of catalysts with (i) Brønsted-type acidity (H-mordenite and Al/P mixed oxide), (ii) Lewis-type acidity (Al trifluoride) or (iii) basic characteristics (Mg/Fe mixed oxide) were investigated in the gas-phase methylation of catechol. When methanol was used as the methylating agent, H-mordenite and AlF₃ gave high selectivities to guaiacol (the product of O-methylation) under mild reaction conditions, that is at very low catechol conversions. An increase in temperature led to the transformation of guaiacol to phenol and cresols, and to considerable catalyst deactivation. The basic catalyst Mg/Fe/O also favored an extensive degradation of guaiacol to phenol. On the mildly acidic catalyst Al/P mixed oxide a stable catalytic performance and a high selectivity to guaiacol at 40% catechol conversion were obtained. When methylformate, a more reactive methylating agent, was used with AlF₃ and Mg/Fe mixed oxide as catalysts, higher catechol conversions and slower deactivation rates could be achieved under mild reaction conditions, with a low extent of guaiacol degradation. However, methylformate rapidly decomposed when temperatures above 350 °C were used. Finally, tests were made by reacting catechol and diethoxymethane with acid catalysts, with the aim of synthesizing methylenedioxybenzene. The latter product was obtained with high selectivity, but with very low yield, due to both catalyst deactivation and decomposition of diethoxymethane.     

When a Tritrophic Interaction Goes Wrong to the Third Level: Xanthoxylin From Trees Causes the Honeybee Larval Mortality in Colonies Affected by the River Disease

The “River Disease” (RD), a disorder impacting honeybee colonies located close to waterways with abundant riparian vegetation (including Sebastiania schottiana, Euphorbiaceae), kills newly hatched larvae. Forager bees from RD-affected colonies collect honeydew excretions from Epormenis cestri (Hemiptera: Flatidae), a planthopper feeding on trees of S. schottiana. First-instar honeybee larvae fed with this honeydew died. Thus, we postulated that the nectars of RD-affected colonies had a natural toxin coming from either E. cestri or S. schottiana. An untargeted metabolomics characterization of fresh nectars extracts from colonies with and without RD allowed to pinpoint xanthoxylin as one of the chemicals present in higher amounts in nectar from RD-affected colonies than in nectars from healthy colonies. Besides, xanthoxylin was also found in the aerial parts of S. schottiana and the honeydew excreted by E. cestri feeding on this tree. A larva feeding assay where xanthoxylin-enriched diets were offered to 1^st instar larvae showed that larvae died in the same proportion as larvae did when offered enriched diets with nectars from RD-colonies. These findings demonstrate that a xenobiotic can mimic the RD syndrome in honeybee larvae and provide evidence of an interspecific flow of xanthoxylin among three trophic levels. Further, our results give information that can be considered when implementing measures to control this honeybee disease.

     

Design of a decision support system for machine tool selection based on machine characteristics and performance tests

Economic globalization, together with heightened market competition and increasingly short product life cycles are motivating companies to use advanced manufacturing technologies. Use of high speed machining is increasingly widespread; however, as the technology is relatively new, it lacks a deep-rooted knowledge base which would facilitate implementation. One of the most frequent problems facing companies wishing to adopt this technology is selecting the most appropriate machine tool for the product in question and own enterprise characteristics. This paper presents a decision support system for high speed milling machine tool selection based on machine characteristics and performance tests. Profile machining tests are designed and conducted in participating machining centers. The decision support system is based on product dimension accuracy, process parameters such as feed rate and interpolation scheme used by CNC and machine characteristics such as machine accuracy and cost. Experimental data for process error and cycle operation time are obtained from profile machining tests with different geometrical feature zones that are often used in manufacturing of discrete parts or die/moulds. All those input parameters have direct impact on productivity and manufacturing cost. Artificial neural network models are utilized for decision support system with reasonable prediction capability.     

Data challenges of time domain astronomy

Astronomy has been at the forefront of the development of the techniques and methodologies of data intensive science for over a decade with large sky surveys and distributed efforts such as the Virtual Observatory. However, it faces a new data deluge with the next generation of synoptic sky surveys which are opening up the time domain for discovery and exploration. This brings both new scientific opportunities and fresh challenges, in terms of data rates from robotic telescopes and exponential complexity in linked data, but also for data mining algorithms used in classification and decision making. In this paper, we describe how an informatics-based approach—part of the so-called “fourth paradigm” of scientific discovery—is emerging to deal with these. We review our experiences with the Palomar-Quest and Catalina Real-Time Transient Sky Surveys; in particular, addressing the issue of the heterogeneity of data associated with transient astronomical events (and other sensor networks) and how to manage and analyze it.     

Initial pH influences microbial communities composition in dark fermentation of scotta permeate

This study addresses for the first time the influence of initial pH on the evolution of microbial consortia in dark fermentation of scotta permeate, using a high-throughput sequencing approach. Three fermentation phases could be detected: 1) a lag phase with no substantial differences in microbial composition at different initial pH values; 2) an exponential H₂ production phase, accompanied by a general increase of Clostridium genus components and higher incidence of Trichococcus genus at neutral and alkaline pH; 3) a final stationary phase, characterized by a general increase of Bifidobacterium and Lactobacillus genera in all reactors. The initial pH value influenced the relative abundance of Trichococcus at 16–48 h of incubation. The metabolic activity of this genus increased the amount of metabolic precursors of H₂ so that, when pH lowered to 5.4, clostridia in the reactors with initial alkaline pH become more active H₂-producers than those in the others.     

Physical,dynamic-mechanical and thermogravimetric analysis of aromatic and cycloaliphatic-based poly(urethaneurea)s

Experimental batches of linear rubber-like polyurethanes characterized by the presence of chemically different hard segments are studied and their thermal and dynamic-mechanical properties are related to the differences in chemical compositions. Interesting correlations are found between the development of crystallinity in such elastomeric poly(urethaneurea)s and the aromatic or alicyclic nature of the diisocyanate. Moreover, for a fixed ratio between hard and soft segments, and for a given composition of the soft segment, the results seem to indicate a better degree of phase separation in cycloaliphatic-based hard segment poly(urethaneurea)s than in aromatic-based hard segment poly(urethaneurea)s.     

Novel Therapeutic Opportunities in Neoadjuvant Setting in Urothelial Cancers: A New Horizon Opened by Molecular Classification and Immune Checkpoint Inhibitors

Muscle invasive bladder cancer (MIBC) is a widespread malignancy with a worse prognosis often related to a late diagnosis. For early-stage MIBC pts, a multidisciplinary approach is mandatory to evaluate the timing of neoadjuvant chemotherapy (NAC) and surgery. The current standard therapy is platinum-based NAC (MVAC-methotrexate, vinblastine, doxorubicin, and cisplatin or Platinum–Gemcitabine regimens) followed by radical cystectomy (RC) with lymphadenectomy. However, preliminary data from Vesper trial highlighted that dose-dense NAC MVAC is endowed with a good pathological response but shows low tolerability. In the last few years, translational-based research approaches have identified several candidate biomarkers of NAC esponsiveness, such as ERCC2, ERBB2, or DNA damage response (DDR) gene alterations. Moreover, the recent consensus MIBC molecular classification identified six molecular subtypes, characterized by different sensitivity to chemo- or targeted or immunotherapy, that could open a novel procedure for patient selection and also for neoadjuvant therapies. The Italian PURE-01 phase II Trial extended data on efficacy and resistance to Immune Checkpoint Inhibitors (ICIs) in this setting. In this review, we summarize the most relevant literature data supporting NAC use in MIBC, focusing on novel therapeutic strategies such as immunotherapy, considering the better patient stratification and selection emerging from novel molecular classification.     

Initial pH influences in-batch hydrogen production from scotta permeate

We studied the influence of initial pH on hydrogen (H₂) production using permeate from scotta (a partially deproteinized cheese whey from ricotta production) as substrate (51 g L^?1 lactose). Dark fermentation was carried out at 35 °C in laboratory batch reactors, in an unbuffered system. Hydrogen production and metabolite (volatile fatty acids, ethanol, and lactic acid) evolution during a 96-h period were monitored in reactors with initial pH varying in the range 4–10. In all reactors, H₂ production started only when pH fell below 6. However, it was much higher (+31%) in the reactors with initial alkaline pH. We conclude that H₂ production occurs only at acidic pH values, but initial alkaline pH values increase the overall H₂ production in dark fermentation of lactose-rich substrates.