Synthesis and coordination chemistry of 2-(di-2-pyridylamino)pyrimidine; structural aspects of spin crossover in an Fe(II) complex

This paper was accepted on February 26 20122-(Di-2-pyridylamino)pyrimidine (L), a potentially ditopic tetradentate ligand, was synthesized from commercially available di-2-pyridylamine and 2-chloropyrimidine. Despite being capable of bridging two metal atoms with bidentate chelation of both metal centres, L prefers to chelate or bridge through the more basic pyridyl donors of the di-2-pyridylamine moiety. Mononuclear trans-[Fe(NCS)2(L)2] and [Cu(L)2(H2O)](BF4)2•H2O complexes, and a discrete [Ag2(L)4](PF6)2 metallomacrocycle were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl2(L)]•(solvate), where solvate = ½H2O or CH2Cl2, was also readily obtained in 71% yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl2)2(L)]•¾H2O complex that was obtained only in very low yield (ca. 3%) from the reaction that produced [PdCl2(L)]•½H2O. trans-[Fe(NCS)2(L)2] undergoes a temperature dependent HS-LS (HS = high spin; LS = low spin) crossover at ca. 205 K that was 2 observed by X-ray crystallography and magnetic measurements and attempts were made to understand the structural basis of this process. Despite efforts to isolate examples of L bridging two iron(II) centres, only the mononuclear trans-[Fe(NCS)2(L)2] species could be obtained.Rachel S. Crees, Boujemma Moubaraki, Keith S. Murray, and Christopher J. Sumb

CO2 × temperature specific early life survival and growth of Menidia menidia assessed by 5 factorial experiments

Dataset: CO2 x temperature effects on Menidia menidia offspringIn five individual rearing experiments, wild-caught M. menidia adults were spawned to test offspring sensitivity to factorial combinations of pCO2 (nominal: 400, 2200, 4000, and 6000 µatm) and temperature (17, 20, 24, and 28 °C) through measurements of early-life survival and growth. For experiment 1, adults were collected from Poquot Beach (40.947376, -73.10258), and the experiment took place at Stony Brook University’s Flax Pond Marine Laboratory. For experiments 2–5, spawning adults were collected from Mumford Cove (41.321526, -72.015247), and experiments were conducted in the Rankin Seawater Facility at University of Connecticut’s Avery Point campus. The experiments quantified two survival and two growth traits for each replicate and CO2 × temperature treatment; embryo survival (fertilization to 1 dph), larval survival (1 dph to experiment termination), size (SL) at hatch (1 dph), and growth rate ((SL at end of experiment – SL 1dph)/number days reared post hatch). These data are published in: Murray, C.S., and Baumann, H. (2018) You Better Repeat It: Complex CO2 × Temperature Effects in Atlantic Silverside Offspring Revealed by Serial experimentation. Diversity. doi:10.3390/d10030069. For a complete list of measurements, refer to the supplemental document 'Field_names.pdf', and a full dataset description is included in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: http://www.bco-dmo.org/dataset/732818NSF Division of Ocean Sciences (NSF OCE) OCE-153633

Prevalence, Awareness, Treatment, and Control of Hypertension in United States Counties, 2001–2009

Hypertension is an important and modifiable risk factor for cardiovascular disease and mortality. Over the last decade, national-levels of controlled hypertension have increased, but little information on hypertension prevalence and trends in hypertension treatment and control exists at the county-level. We estimate trends in prevalence, awareness, treatment, and control of hypertension in US counties using data from the National Health and Nutrition Examination Survey (NHANES) in five two-year waves from 1999–2008 including 26,349 adults aged 30 years and older and from the Behavioral Risk Factor Surveillance System (BRFSS) from 1997–2009 including 1,283,722 adults aged 30 years and older. Hypertension was defined as systolic blood pressure (BP) of at least 140 mm Hg, self-reported use of antihypertensive treatment, or both. Hypertension control was defined as systolic BP less than 140 mm Hg. The median prevalence of total hypertension in 2009 was estimated at 37.6% (range: 26.5 to 54.4%) in men and 40.1% (range: 28.5 to 57.9%) in women. Within-state differences in the county prevalence of uncontrolled hypertension were as high as 7.8 percentage points in 2009. Awareness, treatment, and control was highest in the southeastern US, and increased between 2001 and 2009 on average. The median county-level control in men was 57.7% (range: 43.4 to 65.9%) and in women was 57.1% (range: 43.0 to 65.46%) in 2009, with highest rates in white men and black women. While control of hypertension is on the rise, prevalence of total hypertension continues to increase in the US. Concurrent increases in treatment and control of hypertension are promising, but efforts to decrease the prevalence of hypertension are needed

Targeting matriptase in breast cancer abrogates tumour progression via impairment of stromal-epithelial growth factor signalling.

Matriptase is an epithelia-specific membrane-anchored serine protease that has received considerable attention in recent years because of its consistent dysregulation in human epithelial tumours, including breast cancer. Mice with reduced levels of matriptase display a significant delay in oncogene-induced mammary tumour formation and blunted tumour growth. The abated tumour growth is associated with a decrease in cancer cell proliferation. Here we demonstrate by genetic deletion and silencing that the proliferation impairment in matriptase-deficient breast cancer cells is caused by their inability to initiate activation of the c-Met signalling pathway in response to fibroblast-secreted pro-HGF. Similarly, inhibition of matriptase catalytic activity using a selective small-molecule inhibitor abrogates the activation of c-Met, Gab1 and AKT, in response to pro-HGF, which functionally leads to attenuated proliferation in breast carcinoma cells. We conclude that matriptase is critically involved in breast cancer progression and represents a potential therapeutic target in breast cancer

Evolution of the UV Excess in Early-Type Galaxies

We examine the UV emission from luminous early-type galaxies as a function of redshift. We perform a stacking analysis using Galaxy Evolution Explorer (GALEX) images of galaxies in the NOAO Deep Wide Field Survey (NDWFS) Bo\"otes field and examine the evolution in the UV colors of the average galaxy. Our sample, selected to have minimal ongoing star formation based on the optical to mid-IR SEDs of the galaxies, includes 1843 galaxies spanning the redshift range $0.05\leq z\leq0.65$. We find evidence that the strength of the UV excess decreases, on average, with redshift, and our measurements also show moderate disagreement with previous models of the UV excess. Our results show little evolution in the shape of the UV continuum with redshift, consistent either with the binary model for the formation of Extreme Horizontal Branch (EHB) stars or with no evolution in EHB morphology with look-back time. However, the binary formation model predicts that the strength of the UV excess should also be relatively constant, in contradiction with our measured results. Finally, we see no significant influence of a galaxy's environment on the strength of its UV excess.Comment: 30 pages, 10 figures; accepted by ApJ. Modified from original version to reflect referee's comment

Kinetic and structure–activity studies of the triazolium ion-catalysed benzoin condensation

Steady-state kinetic and structure–activity studies of a series of six triazolium-ion pre-catalysts 2a–2f were investigated for the benzoin condensation. These data provide quantitative insight into the role of triazolium N-aryl substitution under synthetically relevant catalytic conditions in a polar solvent environment. Kinetic behaviour was significantly different to that previously reported for a related thiazolium-ion pre-catalyst 1, with the observed levelling of initial rate constants to νmax at high aldehyde concentrations for all triazolium catalysts. Values for νmax for 2a–2f increase with electron withdrawing N-aryl substituents, in agreement with reported optimal synthetic outcomes under catalytic conditions, and vary by 75-fold across the series. The levelling of rate constants supports a change in rate-limiting step and evidence supports the assignment of the Breslow-intermediate forming step to the plateau region. Correlation of νmax reaction data yielded a positive Hammett ρ-value (ρ = +1.66) supporting the build up of electron density adjacent to the triazolium N-Ar in the rate-limiting step favoured by electron withdrawing N-aryl substituents. At lower concentrations of aldehyde, both Breslow-intermediate and benzoin formation are partially rate-limiting

XBootes: An X-Ray Survey of the NDWFS Bootes Field - Paper I Overview and Initial Results

We obtained a 5 ksec deep Chandra X-ray Observatory ACIS-I map of the 9.3 square degree Bootes field of the NOAO Deep Wide-Field Survey. Here we describe the data acquisition and analysis strategies leading to a catalog of 4642 (3293) point sources with 2 or more (4 or more) counts, corresponding to a limiting flux of roughly 4(8)x10^{-15} erg cm^{-2}s^{-1} in the 0.5-7 keV band. These Chandra XBootes data are unique in that they consitute the widest contiguous X-ray field yet observed to such a faint flux limit. Because of the extraordinarily low background of the ACIS, we expect only 14% (0.7%) of the sources to be spurious. We also detected 43 extended sources in this survey. The distribution of the point sources among the 126 pointings (ACIS-I has a 16 x 16 arcminute field of view) is consistent with Poisson fluctuations about the mean of 36.8 sources per pointing. While a smoothed image of the point source distribution is clumpy, there is no statistically significant evidence of large scale filamentary structure. We do find however, that for theta>1 arcminute, the angular correlation function of these sources is consistent with previous measurements, following a power law in angle with slope -0.7. In a 1.4 deg^{2} sample of the survey, approximately 87% of the sources with 4 or more counts have an optical counterpart to R ~26 mag. As part of a larger program of optical spectroscopy of the NDWFS Bootes area, spectra have been obtained for \~900 of the X-ray sources, most of which are QSOs or AGN.Comment: 18 Pages, 10 figures (AASTex Preprint format

Early Life Socioeconomic Circumstance and Late Life Brain Hyperintensities : A Population Based Cohort Study

Funding: Image acquisition and image analysis for this study was funded by the Alzheimer's Research Trust (now Alzheimer's Research UK). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript. Acknowledgments The authors would like to thank the participants of the Aberdeen 1936 Birth Cohort (ABC36), without whom this research would not have been possible.Peer reviewedPublisher PD