The influence of ambient cure chemistry and stoichiometry on epoxy coating surfaces

The surface properties of epoxy resin coatings influence their function as substrates for subsequent coats. Variation in ambient cure conditions (temperature and relative humidity, RH), stoichiometry (ratio of epoxy: amine) and delay time between epoxy component mixing and film casting (“induction time”) significantly altered the surface properties of ambient cured epoxy resin coatings (Dow Epoxy Novolac D.E.N. 431, resorcinol diglycidyl ether and 4,4-diaminodicyclohexylmethane). Gravimetric analysis showed that increasing induction time significantly reduced surface layer formation (carbamation) of cured epoxy resin coatings at 80% RH but had no measurable effect at 40% RH and below. RMS surface roughness increased with increasing RH and decreased with increasing induction time and ambient cure temperature, at two stoichiometric extremes. However, the net change in surface area arising from these conditions was not sufficient to significantly alter the equilibrium contact angles or wetting regime. We conclude that the observed significant variation in surface wettability was more likely to depend on variation in surface chemistry than roughness; stoichiometry was the variable which most significantly influenced surface wettability, average void volume and fractional free volume, while cure temperature significantly influenced the extent of cure at both stoichiometries. Off-stoichiometry formulation and elevated ambient cure temperature significantly increased system average void volume while fractional free volume decreased, which may be significant for the barrier properties of the final coating

Liquid – liquid phase separation morphologies in ultra-white beetle scales and a synthetic equivalent

Cyphochilus beetle scales are amongst the brightest structural whites in nature, being highly opacifying whilst extremely thin. However, the formation mechanism for the voided intra- scale structure is unknown. Here we report 3D x-ray nanotomography data for the voided chitin networks of intact white scales of Cyphochilus and Lepidiota stigma. Chitin-filling frac- tions are found to be 31 ± 2% for Cyphochilus and 34 ± 1% for Lepidiota stigma, indicating previous measurements overestimated their density. Optical simulations using finite- difference time domain for the chitin morphologies and simulated Cahn-Hilliard spinodal structures show excellent agreement. Reflectance curves spanning filling fraction of 5-95% for simulated spinodal structures, pinpoint optimal whiteness for 25% chitin filling. We make a simulacrum from a polymer undergoing a strong solvent quench, resulting in highly reflective ( 94%) white films. In-situ X-ray scattering confirms the nanostructure is formed through spinodal decomposition phase separation. We conclude that the ultra-white beetle scale nanostructure is made via liquid–liquid phase separation

Impact of clinical phenotypes on management and outcomes in European atrial fibrillation patients: a report from the ESC-EHRA EURObservational Research Programme in AF (EORP-AF) General Long-Term Registry

Background: Epidemiological studies in atrial fibrillation (AF) illustrate that clinical complexity increase the risk of major adverse outcomes. We aimed to describe European AF patients\u2019 clinical phenotypes and analyse the differential clinical course. Methods: We performed a hierarchical cluster analysis based on Ward\u2019s Method and Squared Euclidean Distance using 22 clinical binary variables, identifying the optimal number of clusters. We investigated differences in clinical management, use of healthcare resources and outcomes in a cohort of European AF patients from a Europe-wide observational registry. Results: A total of 9363 were available for this analysis. We identified three clusters: Cluster 1 (n = 3634; 38.8%) characterized by older patients and prevalent non-cardiac comorbidities; Cluster 2 (n = 2774; 29.6%) characterized by younger patients with low prevalence of comorbidities; Cluster 3 (n = 2955;31.6%) characterized by patients\u2019 prevalent cardiovascular risk factors/comorbidities. Over a mean follow-up of 22.5 months, Cluster 3 had the highest rate of cardiovascular events, all-cause death, and the composite outcome (combining the previous two) compared to Cluster 1 and Cluster 2 (all P <.001). An adjusted Cox regression showed that compared to Cluster 2, Cluster 3 (hazard ratio (HR) 2.87, 95% confidence interval (CI) 2.27\u20133.62; HR 3.42, 95%CI 2.72\u20134.31; HR 2.79, 95%CI 2.32\u20133.35), and Cluster 1 (HR 1.88, 95%CI 1.48\u20132.38; HR 2.50, 95%CI 1.98\u20133.15; HR 2.09, 95%CI 1.74\u20132.51) reported a higher risk for the three outcomes respectively. Conclusions: In European AF patients, three main clusters were identified, differentiated by differential presence of comorbidities. Both non-cardiac and cardiac comorbidities clusters were found to be associated with an increased risk of major adverse outcomes

The actin cytoskeleton plays multiple roles in structural colour formation in butterfly wing scales

Abstract Vivid structural colours in butterflies are caused by photonic nanostructures scattering light. Structural colours evolved for numerous biological signalling functions and have important technological applications. Optically, such structures are well understood, however insight into their development in vivo remains scarce. We show that actin is intimately involved in structural colour formation in butterfly wing scales. Using comparisons between iridescent (structurally coloured) and non-iridescent scales in adult and developing H. sara, we show that iridescent scales have more densely packed actin bundles leading to an increased density of reflective ridges. Super-resolution microscopy across three distantly related butterfly species reveals that actin is repeatedly re-arranged during scale development and crucially when the optical nanostructures are forming. Furthermore, actin perturbation experiments at these later developmental stages resulted in near total loss of structural colour in H. sara. Overall, this shows that actin plays a vital and direct templating role during structural colour formation in butterfly scales, providing ridge patterning mechanisms that are likely universal across lepidoptera

Reversible Optical Control of Conjugated Polymer Solubility with Sub-micrometer Resolution

Organic electronics promise to provide flexible, large-area circuitry such as photovoltaics, displays, and light emitting diodes that can be fabricated inexpensively from solutions. A major obstacle to this vision is that most conjugated organic materials are miscible, making solution-based fabrication of multilayer or micro- to nanoscale patterned films problematic. Here we demonstrate that the solubility of prototypical conductive polymer poly(3-hexylthiophene) (P3HT) can be reversibly “switched off” using high electron affinity molecular dopants, then later recovered with light or a suitable dedoping solution. Using this technique, we are able to stack mutually soluble materials and laterally pattern polymer films by evaporation or with light, achieving sub-micrometer, optically limited feature sizes. After forming these structures, the films can be dedoped without disrupting the patterned features; dedoped films have identical optical characteristics, charge carrier mobilities, and NMR spectra as as-cast P3HT films. This method greatly simplifies solution-based device fabrication, is easily adaptable to current manufacturing workflows, and is potentially generalizable to other classes of materials

Auranofin-Mediated NRF2 Induction Attenuates Interleukin 1 Beta Expression in Alveolar Macrophages

Background: Alveolar macrophages (AMs) are resident inflammatory cells in the lung that serve as early sentinels of infection or injury. We have identified thioredoxin reductase 1 inhibition by gold compounds increases activation of nuclear factor erythroid 2-related factor 2 (NRF2)-dependent pathways to attenuate inflammatory responses. The present studies utilized murine alveolar macrophages (MH-S) to test the hypothesis that the gold compound, auranofin (AFN), decreases interleukin (IL)-1β expression through NRF2-mediated interactions with nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) pathway genes and/or increases in glutathione synthesis. Methods: MH-S cells were treated with AFN and lipopolysaccharide (LPS) and analyzed at 6 and 24 h. The Il1b promoter was analyzed by chromatin immunoprecipitation for direct interaction with NRF2. Results: Expression of IL-1β, p-IκBα, p-p65 NF-kB, and NOD-, LRR-, and pyrin domain-containing protein 3 were elevated by LPS exposure, but only IL-1β expression was suppressed by AFN treatment. Both AFN and LPS treatments increased cellular glutathione levels, but attenuation of glutathione synthesis by buthionine sulfoximine (BSO) did not alter expression of Il-1β. Analysis revealed direct NRF2 binding to the Il1b promoter which was enhanced by AFN and inhibited the transcriptional activity of DNA polymerase II. Conclusions: Our data demonstrate that AFN-induced NRF2 activation directly suppresses IL-1β synthesis independent of NFκB and glutathione-mediated antioxidant mechanisms. NRF2 binding to the promoter region of IL1β directly inhibits transcription of the IL1β gene. Collectively, our research suggests that gold compounds elicit NRF2-dependent pulmonary protection by suppressing macrophage-mediated inflammation

Liquid–liquid phase separation morphologies in ultra-white beetle scales and a synthetic equivalent

Cyphochilus beetle scales are amongst the brightest structural whites in nature, being highly opacifying whilst extremely thin. However, the formation mechanism for the voided intra-scale structure is unknown. Here we report 3D x-ray nanotomography data for the voided chitin networks of intact white scales of Cyphochilus and Lepidiota stigma. Chitin-filling fractions are found to be 31 ± 2% for Cyphochilus and 34 ± 1% for Lepidiota stigma, indicating previous measurements overestimated their density. Optical simulations using finite-difference time domain for the chitin morphologies and simulated Cahn-Hilliard spinodal structures show excellent agreement. Reflectance curves spanning filling fraction of 5-95% for simulated spinodal structures, pinpoint optimal whiteness for 25% chitin filling. We make a simulacrum from a polymer undergoing a strong solvent quench, resulting in highly reflective (~94%) white films. In-situ X-ray scattering confirms the nanostructure is formed through spinodal decomposition phase separation. We conclude that the ultra-white beetle scale nanostructure is made via liquid–liquid phase separation.Instrumenten groe