Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

Toxic organic compounds in surface sediments from Elizabeth and Patapsco Rivers and estuaries

This study is an extension of a Chespeake Bay-wide analysis of toxic organic substances into the Elizabeth and Patapsco River subestuaries. Twenty-eight surface sediment samples from the.Elizabeth River and 40 surface sediment samples from the Patapsco, were analyzed in detail for the presence of mainly aromatic and polar organic compounds. Approximately 310 distinct compounds were identified by gas chromatography-mass spectrometry in the Elizabeth River samples, and about 480 in the Patapsco. Total aromatic concentrations ranged from 440,000 to 3,100 ppb in the Elizabeth and from 2.7 x 106 to 6100 ppb in the Patapsco. Similar to observation in the.Chesapeake Bay, unsubstituted polynuclear aromatic hydrocarbons dominated, contributing about 50% to the total resolved concentration. Both subestuaries must be considered to be\u27 severely polluted, and in both there is some evidence of pollutant transport into the Bay

Affine and toric hyperplane arrangements

We extend the Billera-Ehrenborg-Readdy map between the intersection lattice and face lattice of a central hyperplane arrangement to affine and toric hyperplane arrangements. For arrangements on the torus, we also generalize Zaslavsky's fundamental results on the number of regions.Comment: 32 pages, 4 figure

Egg Laying Decisions in Drosophila Are Consistent with Foraging Costs of Larval Progeny

Decision-making is defined as selection amongst options based on their utility, in a flexible and context-dependent manner. Oviposition site selection by the female fly, Drosophila melanogaster, has been suggested to be a simple and genetically tractable model for understanding the biological mechanisms that implement decisions [1]. Paradoxically, female Drosophila have been found to avoid oviposition on sugar which contrasts with known Drosophila feeding preferences [1]. Here we demonstrate that female Drosophila prefer egg laying on sugar, but this preference is sensitive to the size of the egg laying substrate. With larger experimental substrates, females preferred to lay eggs directly on sugar containing media over other (plain, bitter or salty) media. This was in contrast to smaller substrates with closely spaced choices where females preferred non-sweetened media. We show that in small egg laying chambers newly hatched first instar larvae are able to migrate along a diffusion gradient to the sugar side. In contrast, in contexts where females preferred egg laying directly on sugar, larvae were unable to migrate to find the sucrose if released on the sugar free side of the chamber. Thus, where larval foraging costs are high, female Drosophila choose to lay their eggs directly upon the nutritious sugar substrate. Our results offer a powerful model for female decision-making

Dark sectors 2016 Workshop: community report

This report, based on the Dark Sectors workshop at SLAC in April 2016, summarizes the scientific importance of searches for dark sector dark matter and forces at masses beneath the weak-scale, the status of this broad international field, the important milestones motivating future exploration, and promising experimental opportunities to reach these milestones over the next 5-10 years

Phenotypic plasticity of nest-mate recognition cues in formica exsecta ants

It is well established that many ant species have evolved qualitatively distinct species-specific chemical profile that are stable overlarge geographical distances. Within these species profiles quantitative variations in the chemical profile allows distinct colony-specific odours to arise (chemotypes) that are shared by all colony members. This help maintains social cohesion, includingdefence of their colonies against all intruders, including con-specifics. How these colony -level chemotypes are maintainedamong nest-mates has long been debated. The two main theories are; each ant is able to biochemically adjust its chemical profileto‘match’that of its nest-mates and or the queen, or all nest-mates share their individually generated chemical profile viatrophollaxis resulting in an average nest-mate profile. This‘mixing’idea is better known as theGestaltmodel. Unfortunately,it has been very difficult to experimentally test these two ideas in a single experimental design. However, it is now possible usingthe antFormica exsectabecause the compounds used in nest-mate recognition compounds are known. We demonstrate thatworkers adjust their profile to‘match’the dominant chemical profile within that colony, hence maintaining the colony-specificchemotype and indicates that a‘gestalt’mechanism, i.e. profile mixing, plays no or only a minor role

Re-Patterning Sleep Architecture in Drosophila through Gustatory Perception and Nutritional Quality

Organisms perceive changes in their dietary environment and enact a suite of behavioral and metabolic adaptations that can impact motivational behavior, disease resistance, and longevity. However, the precise nature and mechanism of these dietary responses is not known. We have uncovered a novel link between dietary factors and sleep behavior in Drosophila melanogaster. Dietary sugar rapidly altered sleep behavior by modulating the number of sleep episodes during both the light and dark phase of the circadian period, independent of an intact circadian rhythm and without affecting total sleep, latency to sleep, or waking activity. The effect of sugar on sleep episode number was consistent with a change in arousal threshold for waking. Dietary protein had no significant effect on sleep or wakefulness. Gustatory perception of sugar was necessary and sufficient to increase the number of sleep episodes, and this effect was blocked by activation of bitter-sensing neurons. Further addition of sugar to the diet blocked the effects of sweet gustatory perception through a gustatory-independent mechanism. However, gustatory perception was not required for diet-induced fat accumulation, indicating that sleep and energy storage are mechanistically separable. We propose a two-component model where gustatory and metabolic cues interact to regulate sleep architecture in response to the quantity of sugar available from dietary sources. Reduced arousal threshold in response to low dietary availability may have evolved to provide increased responsiveness to cues associated with alternative nutrient-dense feeding sites. These results provide evidence that gustatory perception can alter arousal thresholds for sleep behavior in response to dietary cues and provide a mechanism by which organisms tune their behavior and physiology to environmental cues

Gene expression meta-analysis of Parkinson’s disease and its relationship with Alzheimer’s disease

Abstract Parkinson’s disease (PD) and Alzheimer’s disease (AD) are the most common neurodegenerative diseases and have been suggested to share common pathological and physiological links. Understanding the cross-talk between them could reveal potentials for the development of new strategies for early diagnosis and therapeutic intervention thus improving the quality of life of those affected. Here we have conducted a novel meta-analysis to identify differentially expressed genes (DEGs) in PD microarray datasets comprising 69 PD and 57 control brain samples which is the biggest cohort for such studies to date. Using identified DEGs, we performed pathway, upstream and protein-protein interaction analysis. We identified 1046 DEGs, of which a majority (739/1046) were downregulated in PD. YWHAZ and other genes coding 14–3-3 proteins are identified as important DEGs in signaling pathways and in protein-protein interaction networks (PPIN). Perturbed pathways also include mitochondrial dysfunction and oxidative stress. There was a significant overlap in DEGs between PD and AD, and over 99% of these were differentially expressed in the same up or down direction across the diseases. REST was identified as an upstream regulator in both diseases. Our study demonstrates that PD and AD share significant common DEGs and pathways, and identifies novel genes, pathways and upstream regulators which may be important targets for therapy in both diseases

Cognitive Science of Religion and the Study of Theological Concepts

Abstract The cultural transmission of theological con-cepts remains an underexplored topic in the cognitive sci-ence of religion (CSR). In this paper, I examine whether approaches from CSR, especially the study of content biases in the transmission of beliefs, can help explain the cultural success of some theological concepts. This approach reveals that there is more continuity between theological beliefs and ordinary religious beliefs than CSR authors have hitherto recognized: the cultural transmission of theological concepts is influenced by content biases that also underlie the reception of ordinary religious concepts

Universal DNA methylation age across mammalian tissues

Aging, often considered a result of random cellular damage, can be accurately estimated using DNA methylation profiles, the foundation of pan-tissue epigenetic clocks. Here, we demonstrate the development of universal pan-mammalian clocks, using 11,754 methylation arrays from our Mammalian Methylation Consortium, which encompass 59 tissue types across 185 mammalian species. These predictive models estimate mammalian tissue age with high accuracy (r > 0.96). Age deviations correlate with human mortality risk, mouse somatotropic axis mutations and caloric restriction. We identified specific cytosines with methylation levels that change with age across numerous species. These sites, highly enriched in polycomb repressive complex 2-binding locations, are near genes implicated in mammalian development, cancer, obesity and longevity. Our findings offer new evidence suggesting that aging is evolutionarily conserved and intertwined with developmental processes across all mammals.Publisher PDFPeer reviewe