Unusual Ar-H/Rh-H J(HH) NMR coupling in complexes of rhodium(III): experimental evidence and theoretical support for an eta1-arene structure

The synthesis and structural properties of three new hydridorhodium(III) complexes are reported. Hydrogenolysis of the cyclometalated rhodium dichloride complexes [RhCl2{(S,S)-benbox(Me-2)}] (2a-c) leads to formation of the new complexes [RhCl2(H){(S,S)-ip-benbox(Me-2)H}] (3a-c) in 45% to 85% yield. Compounds 3a-c were found to have unusual features by NMR spectroscopy: in particular, downfield shifted aryl proton resonances (8.88-9.03 ppm) that were coupled to the rhodium hydride resonances. Using X-ray crystallographic studies, a variety of solid- and solution-state characterization techniques, and DFT calculations, these features were attributed to the presence of weak pi-type eta(1)-arene interactions in 3a-c

Weakest-link failure prediction for ceramics

Weakest-link failure prediction for ceramic components is usually based on strength data obtained from 3- and 4-point bend tests. However, in the route from test specimen to actual component several pitfalls are encountered. Firstly, the bend tests themselves do have their problems. Secondly, there is the problem of the interpretation of the uniaxial strength data in terms of a failure criterium for multiaxial stress states, for which at this juncture no universally applicable model is available. In this contribution the difficulties encountered will be summarized. Besides alternatives will be mentioned which are based on microstructural insight and anisotropic deformation models

Physical activity and clustered cardiovascular disease risk factors in young children: a cross-sectional study (the IDEFICS study)

<p>Background The relevance of physical activity (PA) for combating cardiovascular disease (CVD) risk in children has been highlighted, but to date there has been no large-scale study analyzing that association in children aged ≤9 years of age. This study sought to evaluate the associations between objectively-measured PA and clustered CVD risk factors in a large sample of European children, and to provide evidence for gender-specific recommendations of PA.</p> <p>Methods Cross-sectional data from a longitudinal study in 16,224 children aged 2 to 9 were collected. Of these, 3,120 (1,016 between 2 to 6 years, 2,104 between 6 to 9 years) had sufficient data for inclusion in the current analyses. Two different age-specific and gender-specific clustered CVD risk scores associated with PA were determined. First, a CVD risk factor (CRF) continuous score was computed using the following variables: systolic blood pressure (SBP), total triglycerides (TG), total cholesterol (TC)/high-density lipoprotein cholesterol (HDL-c) ratio, homeostasis model assessment of insulin resistance (HOMA-IR), and sum of two skinfolds (score CRFs). Secondly, another CVD risk score was obtained for older children containing the score CRFs + the cardiorespiratory fitness variable (termed score CRFs + fit). Data used in the current analysis were derived from the IDEFICS (‘Identification and prevention of Dietary- and lifestyle-induced health EFfects In Children and infantS’) study.</p> <p>Results In boys <6 years, the odds ratios (OR) for CVD risk were elevated in the least active quintile of PA (OR: 2.58) compared with the most active quintile as well as the second quintile for vigorous PA (OR: 2.91). Compared with the most active quintile, older children in the first, second and third quintiles had OR for CVD risk score CRFs + fit ranging from OR 2.69 to 5.40 in boys, and from OR 2.85 to 7.05 in girls.</p> <p>Conclusions PA is important to protect against clustering of CVD risk factors in young children, being more consistent in those older than 6 years. Healthcare professionals should recommend around 60 and 85 min/day of moderate-to-vigorous PA, including 20 min/day of vigorous PA.</p&gt

Schr\"odinger Holography with and without Hyperscaling Violation

We study the properties of the Schr\"odinger-type non-relativistic holography for general dynamical exponent z with and without hyperscaling violation exponent \theta. The scalar correlation function has a more general form due to general z as well as the presence of \theta, whose effects also modify the scaling dimension of the scalar operator. We propose a prescription for minimal surfaces of this "codimension 2 holography," and demonstrate the (d-1) dimensional area law for the entanglement entropy from (d+3) dimensional Schr\"odinger backgrounds. Surprisingly, the area law is violated for d+1 < z < d+2, even without hyperscaling violation, which interpolates between the logarithmic violation and extensive volume dependence of entanglement entropy. Similar violations are also found in the presence of the hyperscaling violation. Their dual field theories are expected to have novel phases for the parameter range, including Fermi surface. We also analyze string theory embeddings using non-relativistic branes.Comment: 62 pages and 6 figures, v2: several typos in section 5 corrected, references added, v3: typos corrected, references added, published versio

CSMET: Comparative Genomic Motif Detection via Multi-Resolution Phylogenetic Shadowing

Functional turnover of transcription factor binding sites (TFBSs), such as whole-motif loss or gain, are common events during genome evolution. Conventional probabilistic phylogenetic shadowing methods model the evolution of genomes only at nucleotide level, and lack the ability to capture the evolutionary dynamics of functional turnover of aligned sequence entities. As a result, comparative genomic search of non-conserved motifs across evolutionarily related taxa remains a difficult challenge, especially in higher eukaryotes, where the cis-regulatory regions containing motifs can be long and divergent; existing methods rely heavily on specialized pattern-driven heuristic search or sampling algorithms, which can be difficult to generalize and hard to interpret based on phylogenetic principles. We propose a new method: Conditional Shadowing via Multi-resolution Evolutionary Trees, or CSMET, which uses a context-dependent probabilistic graphical model that allows aligned sites from different taxa in a multiple alignment to be modeled by either a background or an appropriate motif phylogeny conditioning on the functional specifications of each taxon. The functional specifications themselves are the output of a phylogeny which models the evolution not of individual nucleotides, but of the overall functionality (e.g., functional retention or loss) of the aligned sequence segments over lineages. Combining this method with a hidden Markov model that autocorrelates evolutionary rates on successive sites in the genome, CSMET offers a principled way to take into consideration lineage-specific evolution of TFBSs during motif detection, and a readily computable analytical form of the posterior distribution of motifs under TFBS turnover. On both simulated and real Drosophila cis-regulatory modules, CSMET outperforms other state-of-the-art comparative genomic motif finders

Holographic Vitrification

We establish the existence of stable and metastable stationary black hole bound states at finite temperature and chemical potentials in global and planar four-dimensional asymptotically anti-de Sitter space. We determine a number of features of their holographic duals and argue they represent structural glasses. We map out their thermodynamic landscape in the probe approximation, and show their relaxation dynamics exhibits logarithmic aging, with aging rates determined by the distribution of barriers.Comment: 100 pages, 25 figure

Can we apply the Mendelian randomization methodology without considering epigenetic effects?

<p>Abstract</p> <p>Introduction</p> <p>Instrumental variable (IV) methods have been used in econometrics for several decades now, but have only recently been introduced into the epidemiologic research frameworks. Similarly, Mendelian randomization studies, which use the IV methodology for analysis and inference in epidemiology, were introduced into the epidemiologist's toolbox only in the last decade.</p> <p>Analysis</p> <p>Mendelian randomization studies using instrumental variables (IVs) have the potential to avoid some of the limitations of observational epidemiology (confounding, reverse causality, regression dilution bias) for making causal inferences. Certain limitations of randomized controlled trials, such as problems with generalizability, feasibility and ethics for some exposures, and high costs, also make the use of Mendelian randomization in observational studies attractive. Unlike conventional randomized controlled trials (RCTs), Mendelian randomization studies can be conducted in a representative sample without imposing any exclusion criteria or requiring volunteers to be amenable to random treatment allocation.</p> <p>Within the last decade, epigenetics has gained recognition as an independent field of study, and appears to be the new direction for future research into the genetics of complex diseases. Although previous articles have addressed some of the limitations of Mendelian randomization (such as the lack of suitable genetic variants, unreliable associations, population stratification, linkage disequilibrium (LD), pleiotropy, developmental canalization, the need for large sample sizes and some potential problems with binary outcomes), none has directly characterized the impact of epigenetics on Mendelian randomization. The possibility of epigenetic effects (non-Mendelian, heritable changes in gene expression not accompanied by alterations in DNA sequence) could alter the core instrumental variable assumptions of Mendelian randomization.</p> <p>This paper applies conceptual considerations, algebraic derivations and data simulations to question the appropriateness of Mendelian randomization methods when epigenetic modifications are present.</p> <p>Conclusion</p> <p>Given an inheritance of gene expression from parents, Mendelian randomization studies not only need to assume a random distribution of alleles in the offspring, but also a random distribution of epigenetic changes (e.g. gene expression) at conception, in order for the core assumptions of the Mendelian randomization methodology to remain valid. As an increasing number of epidemiologists employ Mendelian randomization methods in their research, caution is therefore needed in drawing conclusions from these studies if these assumptions are not met.</p

Comparison of uniaxial and triaxial accelerometry in the assessment of physical activity among adolescents under free-living conditions: the HELENA study

<p>Abstract</p> <p>Background</p> <p>Different types of devices are available and the choice about which to use depends on various factors: cost, physical characteristics, performance, and the validity and intra- and interinstrument reliability. Given the large number of studies that have used uniaxial or triaxial devices, it is of interest to know whether the different devices give similar information about PA levels and patterns. The aim of this study was to compare physical activity (PA) levels and patterns obtained simultaneously by triaxial accelerometry and uniaxial accelerometry in adolescents in free-living conditions.</p> <p>Methods</p> <p>Sixty-two participants, aged 13-16 years, were recruited in this ancillary study, which is a part of the Healthy Lifestyle in Europe by Nutrition in Adolescence (HELENA). All participants wore a uniaxial accelerometer (ActiGraph GT1M^®, Pensacola, FL) and a triaxial accelerometer (RT3^®, Stayhealthy, Monrovia, CA) simultaneously for 7 days. The patterns were calculated by converting accelerometer data output as a percentage of time spent at sedentary, light, moderate, and vigorous PA per day. Analysis of output data from the two accelerometers were assessed by two different tests: Equivalence Test and Bland & Altman method.</p> <p>Results</p> <p>The concordance correlation coefficient between the data from the triaxial accelerometer and uniaxial accelerometer at each intensity level was superior to 0.95. The ANOVA test showed a significant difference for the first three lower intensities while no significant difference was found for vigorous intensity. The difference between data obtained with the triaxial accelerometer and the uniaxial monitor never exceeded 2.1% and decreased as PA level increased. The Bland & Altman method showed good agreement between data obtained between the both accelerometers (<it>p </it>< 0.05).</p> <p>Conclusions</p> <p>Uniaxial and triaxial accelerometers do not differ in their measurement of PA in population studies, and either could be used in such studies.</p