Stereoselective synthesis of the naturally occurring 2-pyranone dodoneine

The first total synthesis of the naturally occurring dihydropyranone dodoneine is reported. Asymmetric allylations were used for the stereoselective generation of the two stereogenic centers. The pyranone ring was created by means of a ringclosing metathesi

Dynamic evolution in the key honey bee pathogen deformed wing virus: Novel insights into virulence and competition using reverse genetics

The impacts of invertebrate RNA virus population dynamics on virulence and infection out- comes are poorly understood. Deformed wing virus (DWV), the main viral pathogen of honey bees, negatively impacts bee health, which can lead to colony death. Despite previ- ous reports on the reduction of DWV diversity following the arrival of the parasitic mite Var- roa destructor, the key DWV vector, we found high genetic diversity of DWV in infested United States honey bee colonies. Phylogenetic analysis showed that divergent US DWV genotypes are of monophyletic origin and were likely generated as a result of diversification after a genetic bottleneck. To investigate the population dynamics of this divergent DWV, we designed a series of novel infectious cDNA clones corresponding to coexisting DWV genotypes, thereby devising a reverse-genetics system for an invertebrate RNA virus qua- sispecies. Equal replication rates were observed for all clone-derived DWV variants in single infections. Surprisingly, individual clones replicated to the same high levels as their mixtures and even the parental highly diverse natural DWV population, suggesting that complemen- tation between genotypes was not required to replicate to high levels. Mixed clone–derived infections showed a lack of strong competitive exclusion, suggesting that the DWV geno- types were adapted to coexist. Mutational and recombination events were observed across clone progeny, providing new insights into the forces that drive and constrain virus diversifi- cation. Accordingly, our results suggest that Varroa influences DWV dynamics by causing an initial selective sweep, which is followed by virus diversification fueled by negative fre- quency-dependent selection for new genotypes. We suggest that this selection might reflect the ability of rare lineages to evade host defenses, specifically antiviral RNA interference (RNAi). In support of this hypothesis, we show that RNAi induced against one DWV strain is less effective against an alternate strain from the same population

Spatial and temporal variability of bacterial communities within a combined sewer system.

This study describes the temporal and spatial variability of bacterial communities within a combined sewer system in England. Sampling was conducted over 9 months in a sewer system with intensive monitoring of hydraulic conditions. The bacterial communities were characterized by 16S rRNA gene-targeted terminal restriction fragment length polymorphism analysis. These data were related to the hydraulic data as well as the sample type, location, and time. Temporal and spatial variation was observed between and within wastewater communities and biofilm communities. The bacterial communities in biofilm were distinctly different from the communities in wastewater and exhibited greater spatial variation, while the wastewater communities exhibited variability between different months of sampling. This study highlights the variation of bacterial communities between biofilm and wastewater, and has shown both spatial and temporal variations in bacterial communities in combined sewers. The temporal variation is of interest for in-sewer processes, for example, sewer odor generation, as field measurements for these processes are often carried out over short durations and may therefore not capture the influence of this temporal variation of the bacterial communities

Examining the Auroral Ionosphere in Three Dimensions Using Reconstructed 2D Maps of Auroral Data to Drive the 3D GEMINI Model

We use the Geospace Environment Model of Ion-Neutral Interactions (GEMINI) to create three-dimensional, time-dependent simulations of auroral ionospheric parameters in the localized, several 100 km region surrounding auroral arcs observed during a winter 2017 sounding rocket campaign, resolving three-dimensional features of fine-scale (km) flow structures in the vicinity of an auroral arc. The three-dimensional calculations of GEMINI allow (with sufficient driving data) auroral current closure to be investigated without idealizing assumptions of sheet-like structures or height integrated ionospheres. Datamaps for two nearly sheet-like arcs are reconstructed from replications of the Isinglass sounding rocket campaign data, and combined with camera-based particle inversions into a set of driving inputs to run the 3D time-dependent model. Comparisons of model results to radar density profiles and to in situ magnetometry observations are presented. Slices of volumetric current, flow, and conductance structures from model outputs are used to interpret closure currents in an auroral arc region, and are compared to original in situ measurements for verification. The predominant source of return current region field aligned current closure for these slow time variation events is seen to be from the conductance gradients, including the Hall. The importance of the versus terms in the determination of the current structure provides a more complicated picture than a previous GEMINI study, which relied predominantly on the divergence of the electric field to determine current structure. Sensitivity of data-driven model results to details of replication and reconstruction processes are discussed, with improvements outlined for future work

Divalent and Multivalent Activation in Phosphate Triesters: A Versatile Method for the Synthesis of Advanced Polyol Synthons

This is the peer reviewed version of the following article: Thomas, C. D., McParland, J. P. and Hanson, P. R. (2009), Divalent and Multivalent Activation in Phosphate Triesters: A Versatile Method for the Synthesis of Advanced Polyol Synthons. Eur. J. Org. Chem., 2009: 5487–5500. doi:10.1002/ejoc.200900560, which has been published in final form at http://doi.org/10.1002/ejoc.200900560. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.The construction of mono- and bicyclic phosphate trimesters possessing divalent and multivalent activation and their subsequent use in the production of advanced polyol synthons is presented. The method highlights efforts to employ phosphate tethers as removable, functionally active tethers capable of multipositional activation and their subsequent role as leaving groups in selective cleavage reactions. The development of phosphate tethers represents an integrated platform for a new and versatile tether for natural product synthesis and sheds light on new approaches to the facile construction of small molecules

Statistical Outliers and Dragon-Kings as Bose-Condensed Droplets

A theory of exceptional extreme events, characterized by their abnormal sizes compared with the rest of the distribution, is presented. Such outliers, called "dragon-kings", have been reported in the distribution of financial drawdowns, city-size distributions (e.g., Paris in France and London in the UK), in material failure, epileptic seizure intensities, and other systems. Within our theory, the large outliers are interpreted as droplets of Bose-Einstein condensate: the appearance of outliers is a natural consequence of the occurrence of Bose-Einstein condensation controlled by the relative degree of attraction, or utility, of the largest entities. For large populations, Zipf's law is recovered (except for the dragon-king outliers). The theory thus provides a parsimonious description of the possible coexistence of a power law distribution of event sizes (Zipf's law) and dragon-king outliers.Comment: Latex file, 16 pages, 1 figur

Recent Applications of Acyclic (Diene)iron Complexes and (Dienyl)iron Cations in Organic Synthesis

Complexation of (tricarbonyl)iron to an acyclic diene serves to protect the ligand against oxidation, reduction, and cycloaddition reactions, whereas the steric bulk of this adjunct serves to direct the approaches of reagents to unsaturated groups attached to the diene onto the face opposite to iron. Furthermore, the Fe(CO)3 moiety can serve to stabilize carbocation centers adjacent to the diene (i.e. pentadienyl-iron cations). Recent applications of these reactivities to the synthesis of polyene-, cyclopropane-, cycloheptadiene-, and cyclohexenone-containing natural products or analogues are presented

The influence of structure on reactivity in alkene metathesis

Abstract Alkene metathesis has grown from a niche technique to a common component of the synthetic organic chemistry toolbox, driven in part by the development of more active catalyst systems, or those optimized for particular purposes. While the range of synthetic chemistry achieved has been exciting, the effects of structure on reactivity have not always been particularly clear, and rarely quantified. Understanding these relationships is important when designing new catalysts, reactions, and syntheses. Here, we examine what is known about the effect of structure on reactivity from two perspectives: the catalyst, and the substrate. The initiation of the precatalyst determines the rate at which active catalyst enters the catalytic cycle; the rate and selectivity of the alkene metathesis reaction is dependent on how the substrate and active catalyst interact. The tools deployed in modern studies of mechanism and structure/activity relationships in alkene metathesis are discussed

Human-wildlife interactions in urban areas: a review of conflicts, benefits and opportunities

Wildlife has existed in urban areas since records began. However, the discipline of urban ecology is relatively new and one that is undergoing rapid growth. All wildlife in urban areas will interact with humans to some degree. With rates of urbanisation increasing globally, there is a pressing need to understand the type and nature of human-wildlife interactions within urban environments, to help manage, mitigate or even promote these interactions. Much research attention has focussed on the core topic of human-wildlife conflict. This inherent bias in the literature is probably driven by the ease with which can be quantified and assessed. Human-wildlife conflicts in terms of disease transmission, physical attack and property damage are important topics to understand, but conversely the benefits of human interactions with wildlife are equally important, becoming increasingly recognised although harder to quantify and generalise. Wildlife may contribute to the provision of ecosystem services in urban areas, and some recent work has shown how interactions with wildlife can provide a range of benefits to health and wellbeing. More research is needed to improve understanding in this area, requiring wildlife biologists to work with other disciplines including economics, public health, sociology, ethics, psychology and planning. There will always be a need to control wildlife populations in certain urban situations to reduce human-wildlife conflict. However, in an increasingly urbanised and resource-constrained world, we need to learn how to manage the risks from wildlife in new ways, and to understand how to maximise the diverse benefits that living with wildlife can bring

The efficacy of transcranial random noise stimulation (tRNS) on mood may depend on individual differences including age and trait mood

Objectives: To assess whether changes in brain microstructures associated with ageing and presence of cardiovascular risk factors (CVRF) reduce the efficacy of transcranial electrical stimulation (tES) improving mood in euthymic older adults. Methods: Using excitatory high-frequency transcranial random noise stimulation (tRNS) over bilateral dorsolateral prefrontal cortex, the effect on mood was assessed in euthymic young adults (YA), older adults (HOA) and older adults with CVRF (OVR). Active-tRNS or sham was applied over two sessions. Positive and Negative Affect Schedule and Warwick Edinburgh Mental Well-being Scale measured self-reported state mood before and after stimulation. Trait mood was also measured using the Geriatric Depression Scale. Results: Response to tRNS seemed dependent on individual differences in age and trait mood. In HOA, more negative trait mood was associated with more positive mood change after tRNS. OVR showed a similar but reduced pattern of mood change to HOA. In YA, more positive trait mood was associated with greater positive mood change after tRNS. Conclusions: Age and trait mood may be important factors when examining the efficacy of tES as an alternative treatment for depression. Significance: Future studies should consider how response to tES is affected by individual differences