As flammable polymeric materials become more ubiquitous in consumer goods, home furnishings, and transportation, there is a growing need for safe and effective flame retardant treatments. Recent ...studies suggest that certain flame retardant chemistries exhibit environmental and health problems, which has prompted the development of new flame retardant technologies. Layer-by-layer assembly has emerged as a promising technique for depositing environmentally-benign flame retardants on a variety of polymeric substrates. This technology has allowed the translation of common flame retardant mechanisms onto the surfaces of flammable polymers in the form of nanometer-scale coatings. Significant reductions in heat release rates and smoke release, as well as the ability to self-extinguish in open flame tests, have been observed on a variety of substrates. This review provides a comprehensive description of flame retardant multilayer nanocoatings on textiles, foams, and bulk polymers, as well as insight into the future direction of this growing field.
Endothelial dysfunction is involved in the development of atherosclerosis, which precedes asymptomatic structural vascular alterations as well as clinical manifestations of cardiovascular disease ...(CVD). Endothelial function can be assessed non-invasively using the flow-mediated dilation (FMD) technique. Flow-mediated dilation represents an endothelium-dependent, largely nitric oxide (NO)-mediated dilatation of conduit arteries in response to an imposed increase in blood flow and shear stress. Flow-mediated dilation is affected by cardiovascular (CV) risk factors, relates to coronary artery endothelial function, and independently predicts CVD outcome. Accordingly, FMD is a tool for examining the pathophysiology of CVD and possibly identifying subjects at increased risk for future CV events. Moreover, it has merit in examining the acute and long-term impact of physiological and pharmacological interventions in humans. Despite concerns about its reproducibility, the available evidence shows that highly reliable FMD measurements can be achieved when specialized laboratories follow standardized protocols. For this purpose, updated expert consensus guidelines for the performance of FMD are presented, which are based on critical appraisal of novel technical approaches, development of analysis software, and studies exploring the physiological principles underlying the technique. Uniformity in FMD performance will (i) improve comparability between studies, (ii) contribute to construction of reference values, and (iii) offer an easy accessible and early marker of atherosclerosis that could complement clinical symptoms of structural arterial disease and facilitate early diagnosis and prediction of CVD outcomes.
In an effort to develop a more environmentally benign flame retardant for polyurethane foam (PUF), layers of halloysite clay nanotubes (HNT) stabilized by branched polyethylenimine (BPEI) or ...poly(acrylic acid) (PAA) are deposited from aqueous suspensions to create multilayered nanocomposite coatings. PUF is very flammable and widely used in upholstered furniture throughout the world. Foam treated with five BPEI‐HNT/PAA‐HNT bilayers, deposited using layer‐by‐layer assembly, is rendered self‐extinguishing in open flame testing. Cone calorimetry reveals that this coating reduces the peak heat release rate (pkHRR) by 62%. Due to the tubular morphology of HNT, small volatile gasses given off during combustion are trapped, so total smoke release (TSR) is reduced by 60%. Infrared spectroscopy suggests this multilayer film survives during combustion, forming an HNT‐rich barrier that prevents mass and energy transfer during open flame testing and calorimetry. The significant reductions in pkHRR and TSR, along with the self‐extinguishing behavior, indicate that these halloysite‐based multilayer films have the potential to greatly improve PUF fire safety. The low cost and natural abundance of HNT makes this technology especially amenable to widespread use.
Multilayer halloysite‐based nanocomposite coatings have been developed for polyurethane foam, dramatically reducing flammability and increasing fire safety using environmentally benign materials. This is the first demonstration of a layer‐by‐layer assembled film containing halloysite nanoclay as a cheap and effective flame retardant, which dramatically reduces heat release rate and total smoke release compared to uncoated foam.
The Gibbs energy, G, determines the equilibrium conditions of chemical reactions and materials stability. Despite this fundamental and ubiquitous role, G has been tabulated for only a small fraction ...of known inorganic compounds, impeding a comprehensive perspective on the effects of temperature and composition on materials stability and synthesizability. Here, we use the SISSO (sure independence screening and sparsifying operator) approach to identify a simple and accurate descriptor to predict G for stoichiometric inorganic compounds with ~50 meV atom
(~1 kcal mol
) resolution, and with minimal computational cost, for temperatures ranging from 300-1800 K. We then apply this descriptor to ~30,000 known materials curated from the Inorganic Crystal Structure Database (ICSD). Using the resulting predicted thermochemical data, we generate thousands of temperature-dependent phase diagrams to provide insights into the effects of temperature and composition on materials synthesizability and stability and to establish the temperature-dependent scale of metastability for inorganic compounds.
We employ quantum chemical calculations to investigate the mechanism of homogeneous CO(2) reduction by pyridine (Py) in the Py/p-GaP system. We find that CO(2) reduction by Py commences with ...PyCOOH(0) formation where: (a) protonated Py (PyH(+)) is reduced to PyH(0), (b) PyH(0) then reduces CO(2) by one electron transfer (ET) via nucleophilic attack by its N lone pair on the C of CO(2), and finally (c) proton transfer (PT) from PyH(0) to CO(2) produces PyCOOH(0). The predicted enthalpic barrier for this proton-coupled ET (PCET) reaction is 45.7 kcal/mol for direct PT from PyH(0) to CO(2). However, when PT is mediated by one to three water molecules acting as a proton relay, the barrier decreases to 29.5, 20.4, and 18.5 kcal/mol, respectively. The water proton relay reduces strain in the transition state (TS) and facilitates more complete ET. For PT mediated by a three water molecule proton relay, adding water molecules to explicitly solvate the core reaction system reduces the barrier to 13.6-16.5 kcal/mol, depending on the number and configuration of the solvating waters. This agrees with the experimentally determined barrier of 16.5 ± 2.4 kcal/mol. We calculate a pK(a) for PyH(0) of 31 indicating that PT preceding ET is highly unfavorable. Moreover, we demonstrate that ET precedes PT in PyCOOH(0) formation, confirming PyH(0)'s pK(a) as irrelevant for predicting PT from PyH(0) to CO(2). Furthermore, we calculate adiabatic electron affinities in aqueous solvent for CO(2), Py, and Py·CO(2) of 47.4, 37.9, and 66.3 kcal/mol respectively, indicating that the anionic complex PyCOO(-) stabilizes the anionic radicals CO(2)(-) and Py(-) to facilitate low barrier ET. As the reduction of CO(2) proceeds through ET and then PT, the pyridine ring becomes aromatic, and thus Py catalyzes CO(2) reduction by stabilizing the PCET TS and the PyCOOH(0) product through aromatic resonance stabilization. Our results suggest that Py catalyzes the homogeneous reductions of formic acid and formaldehyde en route to formation of CH(3)OH through a series of one-electron reductions analogous to the PCET reduction of CO(2) examined here, where the electrode only acts to reduce PyH(+) to PyH(0).
Accessory mineral Eu anomalies (Eu/Eu*) are routinely measured to infer changes in the amount of feldspar over time, allowing accessory mineral U‐Pb dates to be linked to the progressive ...crystallization of igneous and metamorphic rocks and, by extension, geodynamic processes. However, changes in Eu/Eu* can reflect any process that changes the relative availability of Eu2+ and Eu3+. We constructed partitioning budgets for Sm, Eu2+, Eu3+, and Gd in suprasolidus metasedimentary rocks to investigate processes that can influence accessory mineral Eu anomalies. We modeled three scenarios: (1) closed‐system, equilibrium crystallization; (2) fractionation of Eu by feldspar growth during melt crystallization; and (3) removal of Eu by melt extraction. In the closed‐system equilibrium model, accessory mineral Eu/Eu* changes as a function of fO2 and monazite stability; Eu/Eu* changes up to 0.3 over a pressure‐temperature range of 4–12 kbar and 700–950°C. Fractionation of Eu by feldspar growth is modeled to decrease accessory mineral Eu/Eu* by ~0.05–0.15 per 10 wt% feldspar crystallized. Melt extraction has a smaller effect; removal of 10% melt decreases accessory mineral Eu/Eu* in the residue by ≤0.05. Although these models demonstrate that fractionation of Eu by feldspar growth can be a dominant control on a rocks u budget, they also show that the common interpretation that Eu/Eu* only records feldspar growth and breakdown is an oversimplification that could lead to incorrect interpretation about the duration and rates of tectonic processes. Consideration of other processes that influence Eu anomalies will allow for a broader range of geological processes to be investigated by petrochronology.
Plain Language Summary
Metamorphic rocks—rocks in which new minerals grew in response to increase in pressure and temperature related to deep burial or subduction—and igneous rocks—rocks that formed as magmas cool and crystallize—provide a direct record of how Earth's continents have moved and changed through time. To read this record, geologists need to be able to measure the ages of metamorphism and magmatism: When did it happen? How long did it last? How does it relate to other rocks around the world? A common approach to addressing these questions is using U‐Pb dating of the minerals zircon, monazite, and apatite. The elements these minerals incorporate are indicative of how hot and how deep in the Earth they were when they grew. In this study we explore how geologists can use the concentrations of the element Europium (Eu) in these minerals to provide new insights into the geological meaning of U‐Pb dates, leading to more robust interpretations of Earth's plate tectonic history.
Key Points
Eu anomalies in suprasolidus rocks record any process that changes the relative availability of Eu2+ and Eu3+, not just feldspar growth
Disequilibrium is required for feldspar growth to strongly influence accessory mineral Eu anomalies
Comparing accessory mineral Eu anomalies and Sr concentrations leads to more robust interpretation than evaluating Eu anomalies alone
Racial Microaggressions in Everyday Life Sue, Derald Wing; Capodilupo, Christina M; Torino, Gina C ...
The American psychologist,
05/2007, Letnik:
62, Številka:
4
Journal Article
Recenzirano
Racial microaggressions are brief and commonplace daily verbal, behavioral, or environmental indignities, whether intentional or unintentional, that communicate hostile, derogatory, or negative ...racial slights and insults toward people of color. Perpetrators of microaggressions are often unaware that they engage in such communications when they interact with racial/ethnic minorities. A taxonomy of racial microaggressions in everyday life was created through a review of the social psychological literature on aversive racism, from formulations regarding the manifestation and impact of everyday racism, and from reading numerous personal narratives of counselors (both White and those of color) on their racial/cultural awakening. Microaggressions seem to appear in three forms: microassault, microinsult, and microinvalidation. Almost all interracial encounters are prone to microaggressions; this article uses the White counselor - client of color counseling dyad to illustrate how they impair the development of a therapeutic alliance. Suggestions regarding education and training and research in the helping professions are discussed.
We use quantum chemical calculations to elucidate a viable mechanism for pyridine-catalyzed reduction of CO2 to methanol involving homogeneous catalytic steps. The first phase of the catalytic cycle ...involves generation of the key catalytic agent, 1,2-dihydropyridine (PyH2). First, pyridine (Py) undergoes a H(+) transfer (PT) to form pyridinium (PyH(+)), followed by an e(-) transfer (ET) to produce pyridinium radical (PyH(0)). Examples of systems to effect this ET to populate PyH(+)'s LUMO (E(0)(calc) ∼ -1.3 V vs SCE) to form the solution phase PyH(0) via highly reducing electrons include the photoelectrochemical p-GaP system (E(CBM) ∼ -1.5 V vs SCE at pH 5) and the photochemical Ru(phen)3(2+)/ascorbate system. We predict that PyH(0) undergoes further PT-ET steps to form the key closed-shell, dearomatized (PyH2) species (with the PT capable of being assisted by a negatively biased cathode). Our proposed sequential PT-ET-PT-ET mechanism for transforming Py into PyH2 is analogous to that described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics important aspects of the role of NADPH in the formation of C-H bonds in the photosynthetic CO2 reduction process. In particular, in the second phase of the catalytic cycle, which involves three separate reduction steps, we predict that the PyH2/Py redox couple is kinetically and thermodynamically competent in catalytically effecting hydride and proton transfers (the latter often mediated by a proton relay chain) to CO2 and its two succeeding intermediates, namely, formic acid and formaldehyde, to ultimately form CH3OH. The hydride and proton transfers for the first of these reduction steps, the homogeneous reduction of CO2, are sequential in nature (in which the formate to formic acid protonation can be assisted by a negatively biased cathode). In contrast, these transfers are coupled in each of the two subsequent homogeneous hydride and proton transfer steps to reduce formic acid and formaldehyde.
This article presents an overview of the PI3K/Akt/mTOR signaling pathway. As a central regulator of cell growth, protein translation, survival, and metabolism, activation of this signaling pathway ...contributes to the pathogenesis of many tumor types. Biochemical and genetic aberrations of this pathway observed in various cancer types are explored. Last, pathway inhibitors both in development and already approved by the Food and Drug Administration are discussed.
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