Dual Fluorescence and Phosphorescence Emissions from Dye-Modified (NCN)-Bismuth Pincer Thiolate Complexes

We report the synthesis, characterization, and photophysical properties of four new dye-modified (NCN)Bi pincer complexes with two mercaptocoumarin or mercaptopyrene ligands. Their photophysical properties were probed by UV/vis spectroscopy, photoluminescence (PL) studies, and time-dependent density functional theory (TD-DFT) calculations. Absorption spectra of the complexes are dominated by mixed pyrene or coumarin π → π*/n(pS) → pyrene or coumarin π* transitions. While unstable toward reductive elimination of the corresponding disulfide under irradiation at room temperature, the complexes provide stable emissions at 77 K. Under these conditions, coumarin complexes 2 and 4 exhibit exclusively green phosphorescence at 508 nm. In contrast, the emissive properties of pyrene complexes 1 and 3 depend on the excitation wavelength and on sample concentration. Irradiation into the lowest-energy absorption band exclusively triggers red phosphorescence from the pyrenyl residues at 640 nm. At concentrations c < 1 μM, excitation into higher excited electronic states results in blue pyrene fluorescence. With increasing c (1–100 μM), the emission profile changes to dual fluorescence and phosphorescence emission, with a steady increase of the phosphorescence intensity, until at c ≥ 1 mM only red phosphorescence ensues. Progressive red-shifts and broadening of steady-state excitation spectra with increasing sample concentration suggest the presence of static excimers, as we observe it for concentrated solutions of pyrene. Crystalline and powdered samples of 1 indeed show intermolecular association through π-stacking. TD-DFT calculations on model dimers and a tetramer of 1 support the idea of aggregation-induced intersystem crossing (AI-ISC) as the underlying reason for this behavior.publishe

Hepatic Phospholipid Remodeling Modulates Insulin Sensitivity and Systemic Metabolism

Abstract The liver plays a central role in regulating glucose and lipid metabolism. Aberrant insulin action in the liver is a major driver of selective insulin resistance, in which insulin fails to suppress glucose production but continues to activate lipogenesis in the liver, resulting in hyperglycemia and hypertriglyceridemia. The underlying mechanisms of selective insulin resistance are not fully understood. Here It is shown that hepatic membrane phospholipid composition controlled by lysophosphatidylcholine acyltransferase 3 (LPCAT3) regulates insulin signaling and systemic glucose and lipid metabolism. Hyperinsulinemia induced by high‐fat diet (HFD) feeding augments hepatic Lpcat3 expression and membrane unsaturation. Loss of Lpcat3 in the liver improves insulin resistance and blunts lipogenesis in both HFD‐fed and genetic ob/ob mouse models. Mechanistically, Lpcat3 deficiency directly facilitates insulin receptor endocytosis, signal transduction, and hepatic glucose production suppression and indirectly enhances fibroblast growth factor 21 (FGF21) secretion, energy expenditure, and glucose uptake in adipose tissue. These findings identify hepatic LPCAT3 and membrane phospholipid composition as a novel regulator of insulin sensitivity and provide insights into the pathogenesis of selective insulin resistance

Surface tension driven processes densify and retain permeability in magma and lava

We offer new insights into how an explosive eruption can transition into an effusive eruption. Magma containing >0.2 wt% dissolved water has the potential to vesiculate to a porosity in excess of 80 vol.% at atmospheric pressure. Thus all magmas contain volatiles at depth sufficient to form foams and explosively fragment. Yet gas is often lost passively and effusive eruptions ensue. Magmatic foams are permeable and understanding permeability in magma is crucial for models that predict eruptive style. Permeability also governs magma compaction models. Those models generally imply that a reduction in magma porosity and permeability generates an increased propensity for explosivity. Here, our experimental results show that surface tension stresses drive densification without creating an impermeable ‘plug’, offering an additional explanation of why dense magmas can avoid explosive eruption. In both an open furnace and a closed autoclave, we subject pumice samples with initial porosity of ∼70 vol.% to a range of isostatic pressures (0.1–11 MPa) and temperatures (350–950 °C) relevant to shallow volcanic environments. Our experimental data and models constrain the viscosity, permeability, timescales, and length scales over which densification by pore-scale surface tension stresses competes with density-driven compaction. Where surface tension dominates the dynamics, densification halts at a plateau connected porosity of ∼25 vol.% for our samples. SEM, pycnometry and micro-tomography show that in this process (1) microporous networks are destroyed, (2) the relative pore network surface area decreases, and (3) a remaining crystal framework enhances the longevity of macro-pore connectivity and permeability critical for sustained outgassing. We propose that these observations are a consequence of a surface tension-driven retraction of viscous pore walls at areas of high bubble curvature (micro-vesicular network terminations), and that this process drives bulk densification and permits continued outgassing. We propose a regime diagram of the relative dominance of surface tension and gravitational compaction that illustrates the interplay between viscosity, permeability, lengthscale and timescale. We contend that surface tension-driven magma densification is an as-yet overlooked phenomenon that extends our volcanological, geothermal and hydrothermal knowledge of how gas can escape densifying volcanic plugs and why dense lavas remain permeable