Gold(I)-Catalysed Direct Thioetherifications Using Allylic Alcohols: an Experimental and Computational Study

A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (S(N)2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products

Perspectives on the health effects of hurricanes: A review and challenges

Hurricanes are devastating natural disasters which dramatically modify the physical landscape and alter the socio-physical and biochemical characteristics of the environment, thus exposing the affected communities to new environmental stressors, which persist for weeks to months after the hurricane. This paper has three aims. First, it conceptualizes potential direct and indirect health effects of hurricanes and provides an overview of factors that exacerbate the health effects of hurricanes. Second, it summarizes the literature on the health impact of hurricanes. Finally, it examines the time lag between the hurricane (landfall) and the occurrence of diseases. Two major findings emerge from this paper. Hurricanes are shown to cause and exacerbate multiple diseases, and most adverse health impacts peak within six months following hurricanes. However, chronic diseases, including cardiovascular disease and mental disorders, continue to occur for years following the hurricane impact

Inhibition of Chromium(III) Oxidation through Manganese(IV) Oxide Passivation and Iron(II) Abiotic Reduction

Manganese (Mn) oxides are strong oxidants that are ubiquitous in soils and can oxidize redox-active metals, including chromium (Cr). In soil environments, trivalent chromium (Cr(III)) is a benign, immobile micronutrient, whereas the hexavalent Cr(VI) form is present as a highly mobile, toxic chromate oxyanion. Although many studies have characterized the capacity of Mn(III/IV) oxides to oxidize Cr(III) to toxic Cr(VI), the oxidative capacity of Mn oxides in the presence of potentially passivating soil constituents, specifically reduced soluble iron (Fe(II)aq), remains unresolved. We hypothesized that chemical processes at redox interfaces, such as diffusion-limited environments within soil aggregates, can lead to decreased Cr(VI) production from Mn oxide-driven oxidation due to passivation by Fe(II)aq. A multichamber diffusion-limited reactor was used to simulate transport at soil redox interfaces and investigate the capacity of poorly crystalline and crystalline Mn oxides to oxidize solid Cr(III) minerals to Cr(VI) in the presence of Fe(II)aq. As predicted, Cr(VI) was produced through the Mn oxide-catalyzed oxidation of Cr(III) at a rate controlled by the solubility of Cr(OH)3. However, in the presence of Fe(II)aq, the concentration of aqueous Cr(VI) decreased as a function of the Fe(II)aq concentration, where high concentrations of Fe(II)aq completely inhibited Cr(VI) production, likely through both the passivation of the Mn oxide and the direct reduction of Cr(VI) by Fe(II). At both low (14 μM) and high (100 μM) Fe(II)aq concentrations, the iron oxide minerals hematite (Fe2O3) and goethite (α-FeOOH) were associated with the Mn oxides, which can cause surface passivation, a likely role that decreases Cr(III) oxidation. Additionally, the Cr(III) oxidation rate decreased with increasing crystallinity of the Mn oxides whether or not Fe(II) was present

Substituting bouts of sedentary behavior with physical activity: adopting positive lifestyle choices in people with a history of cancer

Purpose: To determine in people with a history of cancer, whether substituting sitting time with other daily activities (i.e., sleeping, walking, moderate and vigorous physical activity) was associated with changes in waist circumference (WC), an important surrogate marker of cardiometabolic risk. Methods: Cross-sectional analyses from the Atlantic Partnership for Tomorrow’s Health (Atlantic PATH) cohort was conducted using isotemporal substitution models to explore the associations of substituting sedentary time, physical activity behavior (International Physical Activity Questionnaire), or sleep (Pittsburgh Sleep Quality Index) with changes in WC. Analyses were conducted using sex-specific WC classifications. Results: In 3,684 people with a history of cancer [mean age (SD) 58.2 (7.3) years; BMI 28.9 (5.2) kgm−2; 71% female], reallocating 10min of sleep or sedentary time for 10min of walking was associated with lower WC in women (p < 0.01). In men, PA intensity appeared to be more strongly associated with a reduced WC. Replacing 10min of sedentary time with 10min of moderate or vigorous PA and replacing 10min of sleep with moderate PA were associated with a significantly reduced WC (p < 0.001). The largest effect was when 10min of moderate PA was replaced with vigorous PA, a reduction in WC (p < 0.01) was evident. Conclusion: For people with a history of cancer, adopting small but positive changes in lifestyle behaviors could help reduce WC and potentially offset negative health-related outcomes associated with higher WC. Further research is required to examine whether such an intervention may be acceptable and manageable among this population

Rapid Screening of Calcium Carbonate Precipitation in the Presence of Amino Acids: Kinetics, Structure, and Composition

Soluble additives are widely used to control crystallization, leading to a definition of properties including size, morphology, polymorph, and composition. However, because of the number of potential variables in these experiments, it is typically extremely difficult to identify reaction conditions—as defined by solution compositions, temperatures, and combinations of additives—that give the desired product. This article introduces a high-throughput methodology which addresses this challenge and enables the streamlined preparation and characterization of crystalline materials. Using calcium carbonate precipitated in the presence of selected amino acids as a model system, we use well plates as microvolume crystallizers, and an accurate liquid-handling pipetting workstation for sample preparation. Following changes in the solution turbidity using a plate reader delivers information about the reaction kinetics, while semiautomated scanning electron microscopy, powder X-ray diffraction, and Raman microscopy provide structural information about the library of crystalline products. Of particular interest for the CaCO3 system is the development of fluorescence-based protocols which rapidly evaluate the amounts of the additives occluded within the crystals. Together, these methods provide a strategy for efficiently screening a broad reaction space, where this can both accelerate the ability to generate crystalline materials with target properties and develop our understanding of additive-directed crystallization

Evolution and expansion of the Mycobacterium tuberculosis PE and PPE multigene families and their association with the duplication of the ESAT-6 (esx) gene cluster regions

BACKGROUND: The PE and PPE multigene families of Mycobacterium tuberculosis comprise about 10% of the coding potential of the genome. The function of the proteins encoded by these large gene families remains unknown, although they have been proposed to be involved in antigenic variation and disease pathogenesis. Interestingly, some members of the PE and PPE families are associated with the ESAT-6 (esx) gene cluster regions, which are regions of immunopathogenic importance, and encode a system dedicated to the secretion of members of the potent T-cell antigen ESAT-6 family. This study investigates the duplication characteristics of the PE and PPE gene families and their association with the ESAT-6 gene clusters, using a combination of phylogenetic analyses, DNA hybridization, and comparative genomics, in order to gain insight into their evolutionary history and distribution in the genus Mycobacterium. RESULTS: The results showed that the expansion of the PE and PPE gene families is linked to the duplications of the ESAT-6 gene clusters, and that members situated in and associated with the clusters represent the most ancestral copies of the two gene families. Furthermore, the emergence of the repeat protein PGRS and MPTR subfamilies is a recent evolutionary event, occurring at defined branching points in the evolution of the genus Mycobacterium. These gene subfamilies are thus present in multiple copies only in the members of the M. tuberculosis complex and close relatives. The study provides a complete analysis of all the PE and PPE genes found in the sequenced genomes of members of the genus Mycobacterium such as M. smegmatis, M. avium paratuberculosis, M. leprae, M. ulcerans, and M. tuberculosis. CONCLUSION: This work provides insight into the evolutionary history for the PE and PPE gene families of the mycobacteria, linking the expansion of these families to the duplications of the ESAT-6 (esx) gene cluster regions, and showing that they are composed of subgroups with distinct evolutionary (and possibly functional) differences

Impact of floral feeding on adult Drosophila suzukii survival and nutrient status

Drosophila suzukii, spotted wing drosophila, is a serious pest of small fruits and cherries in many regions of the world. While host usage has been well studied at the ovipositional and larval feeding stages, little is known about the feeding ecology and nutrient requirements of adults. This study addressed the impact of feeding on the survival and nutrient reserves of adult D. suzukii in laboratory assays. First, access to cherry blossoms increased survival rates of both adult males and females compared to water only. This suggests that these early spring blossoms may provide a food source for D. suzukii in fields that may be devoid of other food sources. Second, D. suzukii reared on a standard laboratory diet as larvae emerged as adults with minimal glycogen and sugar levels. Adults with continued access to a carbohydrate–protein diet showed rapidly elevated carbohydrate reserves, and adults with continued access to only water showed a decline in total sugars. Third, females with access to cherry or blueberry blossoms showed elevated carbohydrate reserves when compared to those with access to water only. These results illustrate the importance of adult feeding in enhancing survival and carbohydrate reserves among D. suzukii.To the best of our knowledge, one or more authors of this paper were federal employees when contributing to this work. This is the publisher’s final pdf, displayed as an "Author's personal copy." The published article is copyrighted by Springer and can be found at: https://doi.org/10.1007/s10340-016-0762-