Overriding Intrinsic Reactivity in Aliphatic C−H Oxidation: Preferential C3/C4 Oxidation of Aliphatic Ammonium Substrates

The site-selective C−H oxidation of unactivated positions in aliphatic ammonium chains poses a tremendous synthetic challenge, for which a solution has not yet been found. Here, we report the preferential oxidation of the strongly deactivated C3/C4 positions of aliphatic ammonium substrates by employing a novel supramolecular catalyst. This chimeric catalyst was synthesized by linking the well-explored catalytic moiety Fe(pdp) to an alkyl ammonium binding molecular tweezer. The results highlight the vast potential of overriding the intrinsic reactivity in chemical reactions by guiding catalysis using supramolecular host structures that enable a precise orientation of the substrates

Decoherence due to contacts in ballistic nanostructures

The active region of a ballistic nanostructure is an open quantum-mechanical system, whose nonunitary evolution (decoherence) towards a nonequilibrium steady state is determined by carrier injection from the contacts. The purpose of this paper is to provide a simple theoretical description of the contact-induced decoherence in ballistic nanostructures, which is established within the framework of the open systems theory. The active region's evolution in the presence of contacts is generally non-Markovian. However, if the contacts' energy relaxation due to electron-electron scattering is sufficiently fast, then the contacts can be considered memoryless on timescales coarsened over their energy relaxation time, and the evolution of the current-limiting active region can be considered Markovian. Therefore, we first derive a general Markovian map in the presence of a memoryless environment, by coarse-graining the exact short-time non-Markovian dynamics of an abstract open system over the environment memory-loss time, and we give the requirements for the validity of this map. We then introduce a model contact-active region interaction that describes carrier injection from the contacts for a generic two-terminal ballistic nanostructure. Starting from this model interaction and using the Markovian dynamics derived by coarse-graining over the effective memory-loss time of the contacts, we derive the formulas for the nonequilibrium steady-state distribution functions of the forward and backward propagating states in the nanostructure's active region. On the example of a double-barrier tunneling structure, the present approach yields an I-V curve with all the prominent resonant features. The relationship to the Landauer-B\"{u}ttiker formalism is also discussed, as well as the inclusion of scattering.Comment: Published versio

Rapid migration from traditional or hybrid to fully virtual education in the age of the coronavirus pandemic: challenges, experiences and views of college and university students

The abrupt outbreak of the coronavirus pandemic throughout the world in March 2020 resulted in the sudden closure of all schools, colleges and universities, institutions, and an unprecedented pivot to remote learning. Students and teachers were confronted with the overwhelming challenge of migrating from the traditional face-to-face or hybrid mode of education to fully virtual learning and assessment environments within an extremely short amount of time. This migration was exceptionally difficult, as it took place halfway through the academic or school year in most countries. While pandemic restrictions currently vary across different regions, the 2020-2021 academic session continues to pose challenges despite the experience gained. In addition to a review of the current state-of-the-art in relation to the effects of COVID-19 on teaching and learning, this paper reports on an empirical study carried out in 26 countries (from Asia, Europe, Africa and America), by 36 academics from 29 academic institutions. Through an extensive global survey of college and university students, information was collected about the challenges (technological, economic, psychological) faced by them, as a result of the pandemic. We also asked the students’ to offer their ideas and suggestions for further improvements in teaching and learning, as we look toward a post-COVID world. In this paper, we address issues relating to the availability of, and accessibility to, necessary digital technologies (e.g., learning and communication platforms), isolation, disconnection, and loneliness among students, the overall impact of the pandemic on learning and academic performance, and the reliability of assessment methods., cybercrime dangers and fake information. A total of 1005 responses to the survey were received and analysed. The results are presented in this paper together with reflections of the authors. The paper concludes with a summary of suggestions for process improvements in distance education, and the need for preventive preparedness in the post-COVID period

Organic Fertilizer Abrasive Grits Increase Soil Available Nitrogen, Plant Height, and Biomass

In organic cropping systems, air‐propelled abrasive grits can be used to control in‐row weeds. If the applied abrasive grit is an approved organic fertilizer, these applications may serve a dual purpose of weed control and crop fertility. Laboratory soil incubations examined the N mineralization rates of several grit types with differing C/N ratios (Agra Grit [crushed walnut shells, 170:1], corncob grit [91:1], Sustane [composted turkey litter, 5.0:1], Phytaboost Plant Food [crushed and pelletized soybean meal, 5.0:1]). A greenhouse study determined plant wheat (Triticum aestivum L.), kale (Brassica napus pabluaria DC), and velvetleaf (Abutilon theophrasti Medik.) growth response in soils amended with these grits. The N mineralization rates varied by grit type, soil, and application rate. The N mineralized from Phytaboost within 56 d was similar among the amounts of N a whereas the amount of N mineralized from Sustane was inversely related to the amount of N applied. Agra Grit and corncob grit immobilized soil N due to their high C/N ratios. In soils amended with Sustane, plant height and biomass were 15–43% and 34–83% greater than for plants grown in soils with Agra Grit, corncob grit, and the nontreated soil. Applications of organic fertilizer as air‐propelled grit may improve crop growth; however, if weed control is imperfect, these grits may increase weed growth. Grits with high C/N ratios may immobilize soil available N but not affect plant growth

Coping strategies in civilians during air attacks

Background Coping strategies may influence the psychological outcome after a stressful event, both as coping at the time of the event and as strategies of dealing with its consequences after the event. The aim of the study was to investigate coping strategies used by civilians during the air attacks in Yugoslavia in 1999, and their association with the level of exposure, gender and psychological symptoms 1 year later. Method The sample is a non-selective group of 139 medical students from the University of Belgrade, Yugoslavia. Open questions and content analysis were used to assess coping strategies. Symptoms of intrusion and avoidance were assessed, as well as general psychological symptoms. Results Content analysis of answers to open questions revealed nine categories of coping strategies (sport and walks, leisure activities, talking and gathering, humor, avoidance, philosophical approach, getting information, work, and substance abuse). A cluster analysis identified three groups of students with different styles of coping. Students that used dominantly 'talking and gathering' had the highest, and the ones that mostly used 'leisure activities' the lowest scores on intrusion. There were significant gender differences in how coping strategies were associated with intrusive symptoms. Conclusion The type of coping strategies used during the air attacks may contribute to the level of intrusive symptoms 1 year after the event. Different coping strategies might be effective in men and women to reduce intrusive symptoms. Longitudinal and prospective studies are needed to draw definite conclusions on causal relationships between coping strategies and levels of posttraumatic stress

A Two-Step Certified Reduced Basis Method

In this paper we introduce a two-step Certified Reduced Basis (RB) method. In the first step we construct from an expensive finite element “truth” discretization of dimension N an intermediate RB model of dimension N≪N . In the second step we construct from this intermediate RB model a derived RB (DRB) model of dimension M≤N. The construction of the DRB model is effected at cost O(N) and in particular at cost independent of N ; subsequent evaluation of the DRB model may then be effected at cost O(M) . The DRB model comprises both the DRB output and a rigorous a posteriori error bound for the error in the DRB output with respect to the truth discretization. The new approach is of particular interest in two contexts: focus calculations and hp-RB approximations. In the former the new approach serves to reduce online cost, M≪N: the DRB model is restricted to a slice or subregion of a larger parameter domain associated with the intermediate RB model. In the latter the new approach enlarges the class of problems amenable to hp-RB treatment by a significant reduction in offline (precomputation) cost: in the development of the hp parameter domain partition and associated “local” (now derived) RB models the finite element truth is replaced by the intermediate RB model. We present numerical results to illustrate the new approach.United States. Air Force Office of Scientific Research (AFOSR Grant number FA9550-07-1-0425)United States. Department of Defense. Office of the Secretary of Defense (OSD/AFOSR Grant number FA9550-09-1-0613)Norwegian University of Science and Technolog

Molecular Characterization of the Gastrula in the Turtle Emys orbicularis: An Evolutionary Perspective on Gastrulation

Due to the presence of a blastopore as in amphibians, the turtle has been suggested to exemplify a transition form from an amphibian- to an avian-type gastrulation pattern. In order to test this hypothesis and gain insight into the emergence of the unique characteristics of amniotes during gastrulation, we have performed the first molecular characterization of the gastrula in a reptile, the turtle Emys orbicularis. The study of Brachyury, Lim1, Otx2 and Otx5 expression patterns points to a highly conserved dynamic of expression with amniote model organisms and makes it possible to identify the site of mesoderm internalization, which is a long-standing issue in reptiles. Analysis of Brachyury expression also highlights the presence of two distinct phases, less easily recognizable in model organisms and respectively characterized by an early ring-shaped and a later bilateral symmetrical territory. Systematic comparisons with tetrapod model organisms lead to new insights into the relationships of the blastopore/blastoporal plate system shared by all reptiles, with the blastopore of amphibians and the primitive streak of birds and mammals. The biphasic Brachyury expression pattern is also consistent with recent models of emergence of bilateral symmetry, which raises the question of its evolutionary significance

Parmodulins Inhibit Thrombus Formation Without Inducing Endothelial Injury Caused by Vorapaxar

Protease-activated receptor-1 (PAR1) couples the coagulation cascade to platelet activation during myocardial infarction and to endothelial inflammation during sepsis. This receptor demonstrates marked signaling bias. Its activation by thrombin stimulates prothrombotic and proinflammatory signaling, whereas its activation by activated protein C (APC) stimulates cytoprotective and antiinflammatory signaling. A challenge in developing PAR1-targeted therapies is to inhibit detrimental signaling while sparing beneficial pathways. We now characterize a novel class of structurally unrelated small-molecule PAR1 antagonists, termed parmodulins, and compare the activity of these compounds to previously characterized compounds that act at the PAR1 ligand–binding site. We find that parmodulins target the cytoplasmic face of PAR1 without modifying the ligand-binding site, blocking signaling through Gαq but not Gα13 in vitro and thrombus formation in vivo. In endothelium, parmodulins inhibit prothrombotic and proinflammatory signaling without blocking APC-mediated pathways or inducing endothelial injury. In contrast, orthosteric PAR1 antagonists such as vorapaxar inhibit all signaling downstream of PAR1. Furthermore, exposure of endothelial cells to nanomolar concentrations of vorapaxar induces endothelial cell barrier dysfunction and apoptosis. These studies demonstrate how functionally selective antagonism can be achieved by targeting the cytoplasmic face of a G-protein–coupled receptor to selectively block pathologic signaling while preserving cytoprotective pathways

On directed interacting animals and directed percolation

We study the phase diagram of fully directed lattice animals with nearest-neighbour interactions on the square lattice. This model comprises several interesting ensembles (directed site and bond trees, bond animals, strongly embeddable animals) as special cases and its collapse transition is equivalent to a directed bond percolation threshold. Precise estimates for the animal size exponents in the different phases and for the critical fugacities of these special ensembles are obtained from a phenomenological renormalization group analysis of the correlation lengths for strips of width up to n=17. The crossover region in the vicinity of the collapse transition is analyzed in detail and the crossover exponent $\phi$ is determined directly from the singular part of the free energy. We show using scaling arguments and an exact relation due to Dhar that $\phi$ is equal to the Fisher exponent $\sigma$ governing the size distribution of large directed percolation clusters.Comment: 23 pages, 3 figures; J. Phys. A 35 (2002) 272