Methane activation and exchange by titanium-carbon multiple bonds

We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)Ti≡C^(t)Bu (A) (PNP^− = N[2-P(CHMe_2)_(2)-4-methylphenyl]_2), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)Ti=CHtBu(CH_3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)Ti=CH_(2)(CH_(2)^(t)Bu), or by forming the methane adduct (PNP)Ti≡C^(t)Bu(CH_4). The thermal, fluxional and chemical behavior of (PNP)Ti=CH^(t)Bu(CH_3) is also presented in this study

Asthma Length of Stay in Hospitals in London 2001–2006: Demographic, Diagnostic and Temporal Factors

Asthma is a condition of significant public health concern associated with morbidity, mortality and healthcare utilisation. This study identifies key determinants of length of stay (LOS) associated with asthma-related hospital admissions in London, and further explores their effects on individuals. Subjects were primarily diagnosed and admitted for asthma in London between 1st January 2001 and 31st December 2006. All repeated admissions were treated uniquely as independent cases. Negative binomial regression was used to model the effect(s) of demographic, temporal and diagnostic factors on the LOS, taking into account the cluster effect of each patient's hospital attendance in London. The median and mean asthma LOS over the period of study were 2 and 3 days respectively. Admissions increased over the years from 8,308 (2001) to 10,554 (2006), but LOS consistently declined within the same period. Younger individuals were more likely to be admitted than the elderly, but the latter significantly had higher LOS (p<0.001). Respiratory related secondary diagnoses, age, and gender of the patient as well as day of the week and year of admission were important predictors of LOS. Asthma LOS can be predicted by socio-demographic factors, temporal and clinical factors using count models on hospital admission data. The procedure can be a useful tool for planning and resource allocation in health service provision

In-situ Generation and Grain Growth of Ceo2 Nanocrystals in AC/DC Electrical Fields

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Phase stability of lanthanum orthovanadate at high-pressure

When monoclinic monazite-type LaVO4 (space group P21/n) is squeezed up to 12 GPa at room temperature, a phase transition to another monoclinic phase has been found. The structure of the high-pressure phase of LaVO4 is indexed with the same space group (P21/n), but with a larger unit-cell in which the number of atoms is doubled. The transition leads to an 8% increase in the density of LaVO4. The occurrence of such a transition has been determined by x-ray diffraction, Raman spectroscopy, and ab initio calculations. The combination of the three techniques allows us to also characterize accurately the pressure evolution of unit-cell parameters and the Raman (and IR)-active phonons of the low- and high-pressure phase. In particular, room-temperature equations of state have been determined. The changes driven by pressure in the crystal structure induce sharp modifications in the color of LaVO4 crystals, suggesting that behind the monoclinic-to-monoclinic transition there are important changes of the electronic properties of LaVO4.Comment: 39 pages, 6 tables, 7 figure

Numerical propagation of high energy cosmic rays in the Galaxy I: technical issues

We present the results of a numerical simulation of propagation of cosmic rays with energy above $10^{15}$ eV in a complex magnetic field, made in general of a large scale component and a turbulent component. Several configurations are investigated that may represent specific aspects of a realistic magnetic field of the Galaxy, though the main purpose of this investigation is not to achieve a realistic description of the propagation in the Galaxy, but rather to assess the role of several effects that define the complex problem of propagation. Our simulations of Cosmic Rays in the Galaxy will be presented in Paper II. We identified several effects that are difficult to interpret in a purely diffusive approach and that play a crucial role in the propagation of cosmic rays in the complex magnetic field of the Galaxy. We discuss at length the problem of the extrapolation of our results to much lower energies where data are available on the confinement time of cosmic rays in the Galaxy. The confinement time and its dependence on particles' rigidity are crucial ingredients for 1) relating the source spectrum to the observed cosmic ray spectrum; 2) quantifying the production of light elements by spallation; 3) predicting the anisotropy as a function of energy.Comment: 29 pages, 12 figures, submitted to JCA

parSMURF, a high-performance computing tool for the genome-wide detection of pathogenic variants.

BACKGROUND: Several prediction problems in computational biology and genomic medicine are characterized by both big data as well as a high imbalance between examples to be learned, whereby positive examples can represent a tiny minority with respect to negative examples. For instance, deleterious or pathogenic variants are overwhelmed by the sea of neutral variants in the non-coding regions of the genome: thus, the prediction of deleterious variants is a challenging, highly imbalanced classification problem, and classical prediction tools fail to detect the rare pathogenic examples among the huge amount of neutral variants or undergo severe restrictions in managing big genomic data. RESULTS: To overcome these limitations we propose parSMURF, a method that adopts a hyper-ensemble approach and oversampling and undersampling techniques to deal with imbalanced data, and parallel computational techniques to both manage big genomic data and substantially speed up the computation. The synergy between Bayesian optimization techniques and the parallel nature of parSMURF enables efficient and user-friendly automatic tuning of the hyper-parameters of the algorithm, and allows specific learning problems in genomic medicine to be easily fit. Moreover, by using MPI parallel and machine learning ensemble techniques, parSMURF can manage big data by partitioning them across the nodes of a high-performance computing cluster. Results with synthetic data and with single-nucleotide variants associated with Mendelian diseases and with genome-wide association study hits in the non-coding regions of the human genome, involhing millions of examples, show that parSMURF achieves state-of-the-art results and an 80-fold speed-up with respect to the sequential version. CONCLUSIONS: parSMURF is a parallel machine learning tool that can be trained to learn different genomic problems, and its multiple levels of parallelization and high scalability allow us to efficiently fit problems characterized by big and imbalanced genomic data. The C++ OpenMP multi-core version tailored to a single workstation and the C++ MPI/OpenMP hybrid multi-core and multi-node parSMURF version tailored to a High Performance Computing cluster are both available at https://github.com/AnacletoLAB/parSMURF

Fragments of the nonlytic proline-rich antimicrobial peptide Bac5 kill Escherichia coli cells by inhibiting protein synthesis

Unlike most antimicrobial peptides (AMPs), the main mode of action of the subclass of proline-rich antimicrobial peptides (PrAMPs) is not based on disruption of the bacterial membrane. Instead, PrAMPs exploit the inner membrane transporters SbmA and YjiL/MdtM to pass through the bacterial membrane and enter the cytosol of specific Gram-negative bacteria, where they exert an inhibitory effect on protein synthesis. Despite sharing a high proline and arginine content with other characterized PrAMPs, the PrAMP Bac5 has a low sequence identity with them. Here we investigated the mode of action of three N-terminal Bac5 fragments, Bac5(1-15), Bac5(1-25), and Bac5(1-31). We show that Bac5(1-25) and Bac5(1-31) retained excellent antimicrobial activity toward Escherichia coli and low toxicity toward eukaryotic cells, whereas Bac5(1-15) was inactive. Bac5(1-25) and Bac5(1-31) inhibited bacterial protein synthesis in vitro and in vivo. Competition assays suggested that the binding site of Bac5 is within the ribosomal tunnel, where it prevents the transition from the initiation to the elongation phase of translation, as reported for other PrAMPs, such as the bovine PrAMP Bac7. Surprisingly, unlike Bac7, Bac5(1-25) exhibited speciesspecific inhibition, being an excellent inhibitor of protein synthesis on E. coli ribosomes but a poor inhibitor on Thermus thermophilus ribosomes. This indicates that while Bac5 most likely has an overlapping binding site with Bac7, the mode of interaction is distinct, suggesting that Bac5 fragments may be interesting alternative lead compounds for the development of new antimicrobial agents

Early Postoperative Exposure to High-Fat Diet Does Not Increase Long-Term Weight Loss or Fat Avoidance After Roux-en-Y Gastric Bypass in Rats

BackgroundBariatric surgery alters food preferences in rats and reportedly decreases desire to consume high-fat high-sugar food in humans. The aim of this study was to investigate whether early post-operative exposure to high-fat food could increase body weight loss after Roux-en-Y gastric bypass (RYGB) by triggering fat avoidance.MethodsMale Wistar rats underwent either RYGB (n = 15) or sham-operations (n = 16). Preoperatively a standardized 4-choice cafeteria diet [dietary options: low-fat/low-sugar (LFLS), low-fat/high-sugar (LFHS), high-fat/low-sugar (HFLS), high-fat/high-sugar (HFHS)] was offered. First, each option was available for 4 days, thereafter rats were offered the 4 options simultaneously for 3 days preoperatively. Post-surgery, 8 rats in the RYGB- and 8 in the sham-group were exposed to a high-fat content diet (Oatmeal + 30% lard, OM+L) for 10 days, while 7 RYGB rats and 8 sham-rats received OM alone. From the 11th postoperative day, the 4-choice cafeteria diet was reintroduced for 55-days. The intake of all available food items, macronutrients and body weight changes were monitored over 8 weeks. Main outcomes were long-term body-weight and daily change in relative caloric intake during the postoperative cafeteria period compared to the preoperative cafeteria.ResultsDuring the first 12 days of postoperative cafeteria access, RYGB-rats exposed to OM+L had a higher mean caloric intake per day than RYGB rats exposed to OM alone (Δ10 kCal, P$_{adj}$ = 0.004), but this difference between the RYGB groups disappeared thereafter. Consequently, in the last 33 days of the postoperative cafeteria diet, the mean body weight of the RYGB+OM+L group was higher compared to RYGB+OM (Δ51 g, P$_{adj}$ &lt; 0.001). RYGB rats, independently from the nutritional intervention, presented a progressive decrease in daily consumption of calories from fat and increased their daily energy intake mainly from non-sugar carbohydrates. No such differences were detected in sham-operated controls exposed to low- or high fat postoperative interventions.ConclusionA progressive decrease in daily fat intake over time was observed after RYGB, independently from the nutritional intervention. This finding confirms that macronutrient preferences undergo progressive changes over time after RYGB and supports the role of ingestive adaptation and learning. Early postoperative exposure to high-fat food failed to accentuate fat avoidance and did not lead to superior weight loss in the long-term

Discovery of soft and hard X-ray time lags in low-mass AGNs

The scaling relations between the black hole (BH) mass and soft lag properties for both active galactic nuclei (AGNs) and BH X-ray binaries (BHXRBs) suggest the same underlying physical mechanism at work in accreting BH systems spanning a broad range of mass. However, the low-mass end of AGNs has never been explored in detail. In this work, we extend the existing scaling relations to lower-mass AGNs, which serve as anchors between the normal-mass AGNs and BHXRBs. For this purpose, we construct a sample of low-mass AGNs ($M_{\rm BH}<3\times 10^{6} M_{\rm \odot}$) from the XMM-Newton archive and measure frequency-resolved time delays between the soft (0.3-1 keV) and hard (1-4 keV) X-ray emissions. We report that the soft band lags behind the hard band emission at high frequencies $\sim[1.3-2.6]\times 10^{-3}$ Hz, which is interpreted as a sign of reverberation from the inner accretion disc in response to the direct coronal emission. At low frequencies ($\sim[3-8]\times 10^{-4}$ Hz), the hard band lags behind the soft band variations, which we explain in the context of the inward propagation of luminosity fluctuations through the corona. Assuming a lamppost geometry for the corona, we find that the X-ray source of the sample extends at an average height and radius of $\sim 10r_{\rm g}$ and $\sim 6r_{\rm g}$, respectively. Our results confirm that the scaling relations between the BH mass and soft lag amplitude/frequency derived for higher-mass AGNs can safely extrapolate to lower-mass AGNs, and the accretion process is indeed independent of the BH mass.Comment: 11 pages, 5 figures, 4 tables, Published in MNRA