On the interaction of acetone with electrophilic metallocavitands having extended cavities

We report the synthesis and characterization of tantalum–boronate trimetallic clusters of general formula {[Cp*Ta]3(μ2-RB(O)2)3(μ2-OH)(μ2-O)2(μ3-OH)} (R= 4-(C6H5)(C6H4) (Ta3-4Ph), 4-(C6H5O)(C6H4) (Ta3-4OPh), 4-(C7H7O)(C6H4) (Ta3-4OBn), 4-(C8H5)(C6H4) (Ta3-4PhEt), and 4-(C12H7)(C6H4) (Ta3-4Napht)). All complexes have been characterized by NMR spectroscopy and X-ray diffraction. The trimetallic species feature a large Lewis acid type cavity allowing for substrate binding in both the solid and the liquid state using a unique electrostatic interaction and a hydrogen bond. ΔH° and ΔS° values for association of acetone with the complexes vary between −2.0 and −4.1 kcal·mol–1 and −3 and 2 cal·mol–1·K–1, respectively, showing weaker binding than smaller cavitands of the same type. The barrier for acetone exchange at equilibrium is similar for all complexes, and ΔH‡ values vary between 8.2 and 11.4 kcal·mol–1

Secular trends of cardiorespiratory fitness in children and adolescents over a 35-year period: Chronicle of a predicted foretold

BackgroundIn the context of concerns regarding the cardiorespiratory fitness (CRF) of youth populations, the aims of this study were: (1) to update reference values for the VO2max for school-aged Canadians and (2) to document secular trends in CRF after a 35-year interval.MethodsBetween September 2014 and April 2017, the CRF of 3725 students (53.2% boys; 6.0 to 17.9 yrs) was determined using the 20-m shuttle run test. The sample was collected in 36 different schools from six cities of Québec (Canada).ResultsMedian values of VO2max decreased with age in both sexes (p ≤ 0.05). By the age of 10, more than 20% of boys showed VO2max values below the recommended value (42 ml·kg−1·min−1). At the age of 17, that proportion reached 56.8%. A similar proportion of 12 yrs girls (20%) were under the recommended minimal value (37 ml·kg−1·min−1) and that value reached 69.9% at the age of 17. Compared to 1982, the VO2max at age 17 has declined by 18% for boys and 12% for girls. The situation is worse in terms of functional capacity (number of stages completed) with an overall decrease of more than 30%.ConclusionThis study demonstrates that, compared to data obtained using the same methodology 35 years ago, the CRF and functional capacity of children and adolescents has declined to levels that should raise concerns from a public health perspective. Thus, the development of strategies to promote a physically active lifestyle in youth is more relevant than ever

Global urban environmental change drives adaptation in white clover

Urbanization transforms environments in ways that alter biological evolution. We examined whether urban environmental change drives parallel evolution by sampling 110,019 white clover plants from 6169 populations in 160 cities globally. Plants were assayed for a Mendelian antiherbivore defense that also affects tolerance to abiotic stressors. Urban-rural gradients were associated with the evolution of clines in defense in 47% of cities throughout the world. Variation in the strength of clines was explained by environmental changes in drought stress and vegetation cover that varied among cities. Sequencing 2074 genomes from 26 cities revealed that the evolution of urban-rural clines was best explained by adaptive evolution, but the degree of parallel adaptation varied among cities. Our results demonstrate that urbanization leads to adaptation at a global scale

Search for gravitational-lensing signatures in the full third observing run of the LIGO-Virgo network

Gravitational lensing by massive objects along the line of sight to the source causes distortions of gravitational wave-signals; such distortions may reveal information about fundamental physics, cosmology and astrophysics. In this work, we have extended the search for lensing signatures to all binary black hole events from the third observing run of the LIGO--Virgo network. We search for repeated signals from strong lensing by 1) performing targeted searches for subthreshold signals, 2) calculating the degree of overlap amongst the intrinsic parameters and sky location of pairs of signals, 3) comparing the similarities of the spectrograms amongst pairs of signals, and 4) performing dual-signal Bayesian analysis that takes into account selection effects and astrophysical knowledge. We also search for distortions to the gravitational waveform caused by 1) frequency-independent phase shifts in strongly lensed images, and 2) frequency-dependent modulation of the amplitude and phase due to point masses. None of these searches yields significant evidence for lensing. Finally, we use the non-detection of gravitational-wave lensing to constrain the lensing rate based on the latest merger-rate estimates and the fraction of dark matter composed of compact objects

Search for eccentric black hole coalescences during the third observing run of LIGO and Virgo

Despite the growing number of confident binary black hole coalescences observed through gravitational waves so far, the astrophysical origin of these binaries remains uncertain. Orbital eccentricity is one of the clearest tracers of binary formation channels. Identifying binary eccentricity, however, remains challenging due to the limited availability of gravitational waveforms that include effects of eccentricity. Here, we present observational results for a waveform-independent search sensitive to eccentric black hole coalescences, covering the third observing run (O3) of the LIGO and Virgo detectors. We identified no new high-significance candidates beyond those that were already identified with searches focusing on quasi-circular binaries. We determine the sensitivity of our search to high-mass (total mass M>70 M⊙) binaries covering eccentricities up to 0.3 at 15 Hz orbital frequency, and use this to compare model predictions to search results. Assuming all detections are indeed quasi-circular, for our fiducial population model, we place an upper limit for the merger rate density of high-mass binaries with eccentricities 0<e≤0.3 at 0.33 Gpc−3 yr−1 at 90\% confidence level

Ultralight vector dark matter search using data from the KAGRA O3GK run

Among the various candidates for dark matter (DM), ultralight vector DM can be probed by laser interferometric gravitational wave detectors through the measurement of oscillating length changes in the arm cavities. In this context, KAGRA has a unique feature due to differing compositions of its mirrors, enhancing the signal of vector DM in the length change in the auxiliary channels. Here we present the result of a search for U(1)B−L gauge boson DM using the KAGRA data from auxiliary length channels during the first joint observation run together with GEO600. By applying our search pipeline, which takes into account the stochastic nature of ultralight DM, upper bounds on the coupling strength between the U(1)B−L gauge boson and ordinary matter are obtained for a range of DM masses. While our constraints are less stringent than those derived from previous experiments, this study demonstrates the applicability of our method to the lower-mass vector DM search, which is made difficult in this measurement by the short observation time compared to the auto-correlation time scale of DM

The kainic acid model of temporal lobe epilepsy

The kainic acid model of temporal lobe epilepsy has greatly contributed to the understanding of the molecular, cellular and pharmacological mechanisms underlying epileptogenesis and ictogenesis. This model presents with neuropathological and electroencephalographic features that are seen in patients with temporal lobe epilepsy. It is also characterized by a latent period that follows the initial precipitating injury (i.e., status epilepticus) until the appearance of recurrent seizures, as observed in the human condition. Finally, the kainic acid model can be reproduced in a variety of species using either systemic, intrahippocampal or intra-amygdaloid administrations. In this review, we describe the various methodological procedures and evaluate their differences with respect to the behavioral, electroencephalographic and neuropathological correlates. In addition, we compare the kainic acid model with other animal models of temporal lobe epilepsy such as the pilocarpine and the kindling model. We conclude that the kainic acid model is a reliable tool for understanding temporal lobe epilepsy, provided that the differences existing between methodological procedures are taken into account. (C) 2013 Elsevier Ltd. All rights reserved

Animal models of temporal lobe epilepsy following systemic chemoconvulsant administration

International audienceIn order to understand the pathophysiology of temporal lobe epilepsy (TLE), and thus to develop new pharmacological treatments, in vivo animal models that present features similar to those seen in TLE patients have been developed during the last four decades. Some of these models are based on the systemic administration of chemoconvulsants to induce an initial precipitating injury (status epilepticus) that is followed by the appearance of recurrent seizures originating from limbic structures. In this paper we will review two chemically-induced TLE models, namely the kainic acid and pilocarpine models, which have been widely employed in basic epilepsy research. Specifically, we will take into consideration their behavioral, electroencephalographic and neuropathologic features. We will also evaluate the response of these models to anti-epileptic drugs and the impact they might have in developing new treatments for TLE. (C) 2015 Elsevier B.V. All rights reserved

A comparison between automated detection methods of high-frequency oscillations (80-500 Hz) during seizures

High-frequency oscillations (HFOs, ripples: 80-200 Hz, fast ripples: 250-500 Hz) recorded from the epileptic brain are thought to reflect abnormal network-driven activity. They are also better markers of seizure onset zones compared to interictal spikes. There is thus an increasing number of studies analysing HFOs in vitro, in vivo and in the EEG of human patients with refractory epilepsy. However, most of these studies have focused on HFOs during interictal events or at seizure onset, and few have analysed HFOs during seizures. In this study, we are comparing three different automated methods of HFO detection to two methods of visual analysis, during the pre-ictal, ictal and post-ictal periods on multiple channels using the rat pilocarpine model of temporal lobe epilepsy. The first method (method 1) detected HFOs using the average of the normalised period, the second (method 2) detected HFOs using the average of the normalised period in 1 s windows and the third (method 3) detected HFOs using the average of a reference period before seizure onset. Overall, methods 2 and 3 showed higher sensitivity compared to method 1. When dividing the analysed traces in pre-, ictal and post-ictal periods, method 3 showed the highest sensitivity during the ictal period compared to method 1, while method 2 was not significantly different from method 1. These findings suggest that method 3 could be used for automated and reliable detection of HFOs on large data sets containing multiple channels during the ictal period. (C) 2012 Elsevier B.V. All rights reserved