Adducts of Lewis acidic stibanes with phosphane chalcogenides.

Starting from ClSbR (R = CF, 3,5-(CF)CH) and H(E)P(Bu) (E = O, S), we prepared the oxy- and sulphanediyl-bridged adducts RSb(Cl)-E-(H)P(Bu), which are stable against the elimination of HCl. The different electron-withdrawing substituents and chalcogen bridging units influence the size of the Sb-E-P angle. ClSb(CF) and BuSnH react to give HSb(CF), which seems to interact weakly with H(O)P(Bu) in solution as observed NMR.

Host-guest chemistry of tridentate Lewis acids based on tribenzotriquinacene.

Flexible poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Hydrosilylation of 4b,8b,12b-triallyltribenzotriquinacene and subsequent exchange of the chlorine substituents with weaker coordinating triflate groups afforded a novel triple silyl-functionalised PLA. By regioselective hydroboration of triallyl-TBTQ with various organoboranes, PLAs with different Lewis acidities were obtained.

Tridentate Lewis Acids Based on Tribenzotriquinacene Chalices.

Chalice-shaped tridentate poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Stannylation of the alkyne units, attached via phenyl-spacers to the benzhydrylic positions to the TBTQ scaffold, with MeNSnMe afforded the trimethyltin substituted TBTQ derivative. Replacement of these tin functions with other elements resulted in rigid boron- and aluminium-functionalised PLAs.

ForCenS-LGM: a dataset of planktonic foraminifera species assemblage composition for the Last Glacial Maximum.

Species assemblage composition of marine microfossils offers the possibility to investigate ecological and climatological change on time scales inaccessible using conventional observations. Planktonic foraminifera - calcareous zooplankton - have an excellent fossil record and are used extensively in palaeoecology and palaeoceanography. During the Last Glacial Maximum (LGM; 19,000 - 23,000 years ago), the climate was in a radically different state.

Identification of the bacterial metabolite aerugine as potential trigger of human dopaminergic neurodegeneration.

The causes of nigrostriatal cell death in idiopathic Parkinson's disease are unknown, but exposure to toxic chemicals may play some role. We followed up here on suggestions that bacterial secondary metabolites might be selectively cytotoxic to dopaminergic neurons. Extracts from Streptomyces venezuelae were found to kill human dopaminergic neurons (LUHMES cells).

A global synthesis of high-resolution stable isotope data from benthic foraminifera of the last deglaciation.

We present the first version of the Ocean Circulation and Carbon Cycling (OC3) working group database, of oxygen and carbon stable isotope ratios from benthic foraminifera in deep ocean sediment cores from the Last Glacial Maximum (LGM, 23-19 ky) to the Holocene (<10 ky) with a particular focus on the early last deglaciation (19-15 ky BP). It includes 287 globally distributed coring sites, with metadata, isotopic and chronostratigraphic information, and age models. A quality check was performed for all data and age models, and sites with at least millennial resolution were preferred.

Ice and ocean constraints on early human migrations into North America along the Pacific coast.

Founding populations of the first Americans likely occupied parts of Beringia during the Last Glacial Maximum (LGM). The timing, pathways, and modes of their southward transit remain unknown, but blockage of the interior route by North American ice sheets between ~26 and 14 cal kyr BP (ka) favors a coastal route during this period. Using models and paleoceanographic data from the North Pacific, we identify climatically favorable intervals when humans could have plausibly traversed the Cordilleran coastal corridor during the terminal Pleistocene.

Volcanic trigger of ocean deoxygenation during Cordilleran ice sheet retreat.

North Pacific deoxygenation events during the last deglaciation were sustained over millennia by high export productivity, but the triggering mechanisms and their links to deglacial warming remain uncertain. Here we find that initial deoxygenation in the North Pacific immediately after the Cordilleran ice sheet (CIS) retreat was associated with increased volcanic ash in seafloor sediments. Timing of volcanic inputs relative to CIS retreat suggests that regional explosive volcanism was initiated by ice unloading.

Photoresponsive Dissipative Macrocycles Using Visible-Light-Switchable Azobenzenes.

Visible light can be used to shift dynamic covalent imine assemblies out of equilibrium. We studied a fluorinated azobenzene building block that reliably undergoes geometric isomerism upon irradiation. The building block was used in combination with two different amines, ethylenediamine and R,R-1,2-diaminocyclohexane, to create a library of imine macrocycles.

Carbon dioxide reduction by an Al-O-P frustrated Lewis pair.

The reaction of BuP(O)H with BisAlH (Bis = CH(SiMe)) afforded the adduct BuP(H)-O-Al(H)Bis (3). It slowly releases H to form the first oxygen-bridged geminal Al/P frustrated Lewis pair BuP-O-AlBis. It is capable of reversibly binding molecular hydrogen to afford 3, shown by NMR and H/D scrambling experiments, and forms a 1,2-adduct with CO.

Noncovalent Synergy: Aurophilicity and Aryl Stacking in Bis(gold(I)aryl)-dmpm Complexes.

Bis(dimethylphosphino)methane (dmpm) was used as a ligand to synthesize four semi-supported dinuclear gold(I) complexes, dmpm(AuR) (R = Cl, CH, CCl, and CF), which were studied concerning the synergistic effects of two weak noncovalent interactions: aurophilic and aryl-aryl stacking interactions. The chloro-substituted complex was synthesized by the ligand substitution of (tht)AuCl with dmpm and further functionalized by the reaction with PhMgBr or generated CClLi to afford the phenyl- and pentachlorophenyl-substituted compounds, respectively. The pentafluorophenyl-substituted gold complex was generated by the ligand substitution of (tht)Au(CF) with dmpm.

Inferred Subcellular Localization of Peroxisomal Matrix Proteins of Suggests an Important Role of Peroxisomes in Cryptophytes.

Peroxisomes participate in several important metabolic processes in eukaryotic cells, such as the detoxification of reactive oxygen species (ROS) or the degradation of fatty acids by β-oxidation. Recently, the presence of peroxisomes in the cryptophyte and other "chromalveolates" was revealed by identifying proteins for peroxisomal biogenesis. Here, we investigated the subcellular localization of candidate proteins of in the diatom , either possessing a putative peroxisomal targeting signal type 1 (PTS1) sequence or factors lacking a peroxisomal targeting signal but known to be involved in β-oxidation.

Enumeration of Public Health Nurses in the United States: Limits of Current Standards.

Recent national initiatives in nursing and public health have emphasized the need for a robust public health nursing (PHN) workforce. In this article, we analyze the extent to which recent national enumeration surveys base their counts of this workforce on the definitions, scope, and standards for practice and practice competencies of the PHN nursing specialty. By and large, enumeration surveys continue to rely on practice setting to define the PHN workforce, which is an insufficient approach for meeting the goals of major nursing and public health initiatives.

Host-guest chemistry of a bidentate silyl-triflate bis-Lewis acid - complex complexation behaviour unravelled by diffusion NMR spectroscopy.

The bidentate silicon-based Lewis acid, bis(dimethyl-(trifluoromethylsulfonyl)silylethyl)dimethylsilane, MeSi[(CH)SiMeOTf], was prepared in a two-step synthesis starting from dimethyldivinylsilane by hydrosilylation with dimethylchlorosilane and subsequent Lewis acidity enhancement of the terminal silicon atoms by substituting the chlorine with triflate groups using silver triflate. The potential of the resulting MeSi[(CH)SiMeOTf] for binding of Lewis basic guests was explored in reactions with mono- and bifunctional aromatic nitrogen bases. A 1 : 2-adduct with pyridine and a 2 : 2-adduct with 4,4'-bipyridine was structurally characterised in the solid state.

Glacial isostatic adjustment directed incision of the Channeled Scabland by Ice Age megafloods.

During the last deglaciation, dozens of glacial outburst floods-among the largest known floods on Earth-scoured the Channeled Scabland landscape of eastern Washington. Over this same period, deformation of the Earth's crust in response to the growth and decay of ice sheets changed the topography by hundreds of meters. Here, we investigated whether glacial isostatic adjustment affected routing of the Missoula floods and incision of the Channeled Scabland from an impounded, glacial Lake Columbia.

Evaluation of the binding mode of a cytotoxic dinuclear nickel complex to two neighboring phosphates of the DNA backbone.

A family of dinuclear complexes based on 2,7-disubstituted 1,8-naphthalenediol-ligands has been designed to bind covalently to two neighboring phosphate diester groups in the backbone of DNA. The dinuclear Cu and Ni complexes bind to DNA resulting in the inhibition of DNA synthesis in PCR experiments and in a cytotoxicity that is stronger for human cancer cells than for human stem cells of the same proliferation rate. These experiments support but cannot prove that the dinuclear complexes bind as intended to two neighboring phosphate ester groups of the DNA backbone.

Monitoring dynamic pre-crystallization aggregation processes in solution by VT-DOSY-NMR spectroscopy.

Equimolar mixtures of pyridine (Py) with -halotetrafluoropyridine (BrTFP and ITFP) were investigated by VT-diffusion NMR experiments. The formation of a halogen-bond-stabilized ITFPPy complex was detected upon cooling a solution in methylcyclohexane- to 260 K; this allows monitoring a halogen-bond-driven aggregation process preceding crystallization in solution.

The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond.

Catechols occupy a unique role in the structural, bio-, and geochemistry of silicon. Although a wealth of knowledge exists on their hypercoordinate complexes, the structure of tetracoordinate bis(catecholato)silane, Si(cat) , has been enigmatic since its first report in 1951. Indeed, the claim of a planar-tetracoordinated silicon in triggered a prominent debate, which is unsettled to this day.

Microscale communication between bacterial pathogens and the host epithelium.

Pathogenic bacteria have evolved a variety of highly selective adhesins allowing these microbes to engage specific surface determinants of their eukaryotic host cells. Receptor clustering induced by the multivalent microorganisms will not only anchor the bacteria to the tissue, but will inevitably trigger host cell signaling. It has become clear, that these bacteria-initiated signaling events can be seen as a form of localized communication with host epithelial cells.

The revised Approved Instructional Resources score: An improved quality evaluation tool for online educational resources.

Background: Free Open-Access Medical education (FOAM) use among residents continues to rise. However, it often lacks quality assurance processes and residents receive little guidance on quality assessment. The Academic Life in Emergency Medicine Approved Instructional Resources tool (AAT) was created for FOAM appraisal by and for expert educators and has demonstrated validity in this context.

Phasing of millennial-scale climate variability in the Pacific and Atlantic Oceans.

New radiocarbon and sedimentological results from the Gulf of Alaska document recurrent millennial-scale episodes of reorganized Pacific Ocean ventilation synchronous with rapid Cordilleran Ice Sheet discharge, indicating close coupling of ice-ocean dynamics spanning the past 42,000 years. Ventilation of the intermediate-depth North Pacific tracks strength of the Asian monsoon, supporting a role for moisture and heat transport from low latitudes in North Pacific paleoclimate. Changes in carbon-14 age of intermediate waters are in phase with peaks in Cordilleran ice-rafted debris delivery, and both consistently precede ice discharge events from the Laurentide Ice Sheet, known as Heinrich events.

Novel glucosinolate metabolism in larvae of the leaf beetle Phaedon cochleariae.

Plants of the Brassicales are defended by a binary system, in which glucosinolates are degraded by myrosinases, forming toxic breakdown products such as isothiocyanates and nitriles. Various detoxification pathways and avoidance strategies have been found that allow different herbivorous insect taxa to deal with the glucosinolate-myrosinase system of their host plants. Here, we investigated how larvae of the leaf beetle species Phaedon cochleariae (Coleoptera: Chrysomelidae), a feeding specialist on Brassicaceae, cope with this binary defence.

Sediment controls dynamic behavior of a Cordilleran Ice Stream at the Last Glacial Maximum.

The uncertain response of marine terminating outlet glaciers to climate change at time scales beyond short-term observation limits models of future sea level rise. At temperate tidewater margins, abundant subglacial meltwater forms morainal banks (marine shoals) or ice-contact deltas that reduce water depth, stabilizing grounding lines and slowing or reversing glacial retreat. Here we present a radiocarbon-dated record from Integrated Ocean Drilling Program (IODP) Site U1421 that tracks the terminus of the largest Alaskan Cordilleran Ice Sheet outlet glacier during Last Glacial Maximum climate transitions.

Sea level fingerprinting of the Bering Strait flooding history detects the source of the Younger Dryas climate event.

During the Last Glacial Maximum, expansive continental ice sheets lowered globally averaged sea level ~130 m, exposing a land bridge at the Bering Strait. During the subsequent deglaciation, sea level rose rapidly and ultimately flooded the Bering Strait, linking the Arctic and Pacific Oceans. Observational records of the Bering Strait flooding have suggested two apparently contradictory scenarios for the timing of the reconnection.

The role of Northeast Pacific meltwater events in deglacial climate change.

Columbia River megafloods occurred repeatedly during the last deglaciation, but the impacts of this fresh water on Pacific hydrography are largely unknown. To reconstruct changes in ocean circulation during this period, we used a numerical model to simulate the flow trajectory of Columbia River megafloods and compiled records of sea surface temperature, paleo-salinity, and deep-water radiocarbon from marine sediment cores in the Northeast Pacific. The North Pacific sea surface cooled and freshened during the early deglacial (19.