Your search

The model reactions CH3X + (NH—CH=O)M ➔ CH3—NH—NH═O or NH═CH—O—CH3 + MX (M = none, Li, Na, K, Ag, Cu; X = F, Cl, Br) are investigated to demonstrate the feasibility of Marcus theory and the hard and soft acids and bases (HSAB) principle in predicting the reactivity of ambident nucleophiles. The delocalization indices (DI) are defined in the framework of the quantum theory of atoms in molecules (QT-AIM), and are used as the scale of softness in the HSAB principle. To react with the ambident nucleophile NH═CH—O−, the carbocation H3C+ from CH3X (F, Cl, Br) is actually a borderline acid according to the DI values of the forming C…N and C…O bonds in the transition states (between 0.25 and 0.49), while the counter ions are divided into three groups according to the DI values of weak interactions involving M (M…X, M…N, and M…O): group I (M = none, and Me4N) basically show zero DI values; group II species (M = Li, Na, and K) have noticeable DI values but the magnitudes are usually less than 0.15; and group III species (M = Ag and Cu(I)) have significant DI values (0.30–0.61). On a relative basis, H3C+ is a soft acid with respect to group I and group II counter ions, and a hard acid with respect to group III counter ions. Therefore, N-regioselectivity is found in the presence of group I and group II counter ions (M = Me4N, Li, Na, K), while O-regioselectivity is observed in the presence of the group III counter ions (M = Ag, and Cu(I)). The hardness of atoms, groups, and molecules is also calculated with new functions that depend on ionization potential (I) and electron affinity (A) and use the atomic charges obtained from localization indices (LI), so that the regioselectivity is explained by the atomic hardness of reactive nitrogen atoms in the transition states according to the maximum hardness principle (MHP). The exact Marcus equation is derived from the simple harmonic potential energy parabola, so that the concepts of activation free energy, intrinsic activation barrier, and reaction energy are completely connected. The required intrinsic activation barriers can be either estimated from ab initio calculations on reactant, transition state, and product of the model reactions, or calculated from identity reactions. The counter ions stabilize the reactant through bridging N- and O-site of reactant of identity reactions, so that the intrinsic barriers for the salts are higher than those for free ambident anions, which is explained by the increased reorganization parameter Δr. The proper application of Marcus theory should quantitatively consider all three terms of Marcus equation, and reliably represent the results with potential energy parabolas for reactants and all products. For the model reactions, both Marcus theory and HSAB principle/MHP principle predict the N-regioselectivity when M = none, Me4N, Li, Na, K, and the O-regioselectivity when M = Ag and Cu(I). © 2019 Wiley Periodicals, Inc. © 2019 Wiley Periodicals, Inc.

We present the discovery from Transiting Exoplanet Survey Satellite (TESS) data of LTT 1445Ab. At a distance of 6.9 pc, it is the second nearest transiting exoplanet system found to date, and the closest one known for which the primary is an M dwarf. The host stellar system consists of three mid-to-late M dwarfs in a hierarchical configuration, which are blended in one TESS pixel. We use MEarth data and results from the Science Processing Operations Center data validation report to determine that the planet transits the primary star in the system. The planet has a radius of, an orbital period of days, and an equilibrium temperature of K. With radial velocities from the High Accuracy Radial Velocity Planet Searcher, we place a 3σ upper mass limit of 8.4 on the planet. LTT 1445Ab provides one of the best opportunities to date for the spectroscopic study of the atmosphere of a terrestrial world. We also present a detailed characterization of the host stellar system. We use high-resolution spectroscopy and imaging to rule out the presence of any other close stellar or brown dwarf companions. Nineteen years of photometric monitoring of A and BC indicate a moderate amount of variability, in agreement with that observed in the TESS light-curve data. We derive a preliminary astrometric orbit for the BC pair that reveals an edge-on and eccentric configuration. The presence of a transiting planet in this system hints that the entire system may be co-planar, implying that the system may have formed from the early fragmentation of an individual protostellar core. © 2019. The American Astronomical Society. All rights reserved..

This book examines the effects that political institutions, the legal system, and economic policies have had on the human rights record in the PRC since 1949. The authors first address the problems of assessing political liberties in a nation that emphasizes economic over civil rights and that has traditionally valued collective rights over individ. © 1988 by Taylor & Francis. All rights reserved.

Laser-induced fluorescence (LIF) technique was used to generate spectral signatures of endogenous fluorophores relevant to the tissue molecular composition changes in human brain glioma tumors. The goal is to study the changes of fluorescence emission spectra from endogenous fluorophores in human brain glioma of different grades, and to find new biomarkers for prognostic optical molecular pathological diagnosis. Two hundred and thirty-seven (237) native fluorescence spectra from 61 subjects were measured using LabRAM HR Evolution micro photoluminescence (PL) system for four grades of glioma tumors in ex-vivo. The differences of four grades of glioma tumors were identified by the characteristic fluorophores fingerprints under the excitation laser wavelength at UV 325nm. To our best knowledge, this is the first report for human brain study using this technique. The fluorescence peaks of biomarkers with major contribution were found, including tryptophan, collagen, elastin, reduced nicotinamide adenine dinucleotide (NADH), flavin adenine dinucleotide (FAD) and phospholipids that play important roles in the cellular energy metabolism and glycolysis pathway. The ratios of peak intensities and the peak positions in fluorescence spectra of may be used to diagnose human brain diseases or to guide biopsy during surgical resection. © 2019 SPIE.

A VRR-LRR analyzer with handheld fiber‐optic probe is reported for the first time for diagnosis of brain GBM in vivo. The sensitivity for identification is 80% compared with histopathology examination. © OSA 2019. The Author(s).

Web applications are built to be accessible to everyone. Unfortunately, many web applications are inaccessible to people with special needs or disabilities. In this work, we show a methodology used to make web applications more accessible to a diverse group of people. The process includes two phases: evaluation and improvement. In the first phase, the Web Accessibility Barrier (WAB) score metric together with the Accessibility Failure Rate (AFR) metric are used to evaluate web applications. In the second phase changes suggested by accessibility checker tool are implemented in the software to enhance the metrics values and reach the target level of accessibility. The open-source chat application, Zulip, is used as a case study to show the effectiveness of this approach. © 2021 IEEE.

Healthy workplaces promote inclusionary behaviors. When nurses experience exclusionary behaviors such as bullying and incivility, there may also be hidden issues with acceptance of diversity in the workplace environment. Educating nursing staff on the importance of variations in age, culture, gender, sex, race, ethnicity, and religion in the workplace can help facilitate communication among staff. For example, organizations can use educational forums to discuss how different cultures vary in the addressing of conflict within the workplace; some cultures may prefer to reach consensus rather than be confrontational. Chapter 5 discusses strategies that nurses and organizations can implement, such as Team Strategies and Tools to Enhance Performance and Patient Safety (TeamSTEPPS). TeamSTEPPS is a curriculum that can be used to improve teamwork skills, communication, and build team collaboration. © 2021, IGI Global.

Global hyperon polarization, P¯H, in Au+Au collisions over a large range of collision energy, sNN, was recently measured and successfully reproduced by hydrodynamic and transport models with intense fluid vorticity of the quark-gluon plasma. While naïve extrapolation of data trends suggests a large P¯H as the collision energy is reduced, the behavior of P¯H at small sNN¡7.7 GeV is unknown. Operating the STAR experiment in fixed-target mode, we measured the polarization of Λ hyperons along the direction of global angular momentum in Au+Au collisions at sNN=3 GeV. The observation of substantial polarization of 4.91±0.81(stat.)±0.15(syst.)% in these collisions may require a reexamination of the viscosity of any fluid created in the collision, of the thermalization timescale of rotational modes, and of hadronic mechanisms to produce global polarization. © 2021 American Physical Society.

According to first-principle lattice QCD calculations, the transition from quark-gluon plasma to hadronic matter is a smooth crossover in the region μB≤Tc. In this range the ratio, C6/C2, of net-baryon distributions are predicted to be negative. In this Letter, we report the first measurement of the midrapidity net-proton C6/C2 from 27, 54.4, and 200 GeV Au+Au collisions at the Relativistic Heavy Ion Collider (RHIC). The dependence on collision centrality and kinematic acceptance in (pT, y) are analyzed. While for 27 and 54.4 GeV collisions the C6/C2 values are close to zero within uncertainties, it is observed that for 200 GeV collisions, the C6/C2 ratio becomes progressively negative from peripheral to central collisions. Transport model calculations without critical dynamics predict mostly positive values except for the most central collisions within uncertainties. These observations seem to favor a smooth crossover in the high-energy nuclear collisions at top RHIC energy. © 2021 American Physical Society.

Purpose: The purpose of this paper is to explore an emerging ethical theory for the Digital Age – Flourishing Ethics – which will likely be applicable in many different cultures worldwide, addressing not only human concerns but also activities, decisions and consequences of robots, cyborgs, artificially intelligent agents and other new digital technologies. Design/methodology/approach: In the past, a number of influential ethical theories in Western philosophy have focused upon choice and autonomy, or pleasure and pain or fairness and justice. These are important ethical concepts, but we consider “flourishing” to be a broader “umbrella concept” under which all of the above ideas can be included, plus additional ethical ideas from cultures in other regions of the world (for example, Buddhist, Muslim, Confucianist cultures and others). Before explaining the applied approach, this study discusses relevant ideas of four example thinkers who emphasize flourishing in their ethics writings: Aristotle, Norbert Wiener, James Moor and Simon Rogerson. Findings: Flourishing Ethics is not a single ethical theory. It is “an approach,” a “family” of similar ethical theories which can be successfully applied to humans in many different cultures, as well as to non-human agents arising from new digital technologies. Originality/value: This appears to be the first extended analysis of the emerging flourishing ethics “family” of theories. © 2021, Emerald Publishing Limited.

Our research objective is to compare the effectiveness of standard online learning methods versus the utilization of virtual reality in education in terms of student focus and information retention. Our proposed platform will have identical lesson plans in virtual reality as our online learning methods. Eye gaze tracking and a recall test will be used on both platforms to measure focus on the screen and retention, respectively. The ultimate goal of the project is to use this data to evaluate the effectiveness of VR as a digital learning environment. © 2021 IEEE.