Environmental Control of Triplet Emission in Donor–Bridge–Acceptor Organometallics

Carbene‐metal‐amides (CMAs) are a promising family of donor–bridge–acceptor molecular charge‐transfer (CT) emitters for organic light‐emitting diodes. A universal approach is demonstrated to tune the energy of their CT emission. A blueshift of up to 210 meV is achievable in solid state via dilution in a polar host matrix. The origin of this shift has two components: constraint of thermally‐activated triplet diffusion, and electrostatic interactions between guest and polar host. This allows the emission of mid‐green CMA archetypes to be tuned to sky blue without chemical modifications. Monte‐Carlo simulations based on a Marcus‐type transfer integral successfully reproduce the concentration‐ and temperature‐dependent triplet diffusion process, revealing a substantial shift in the ensemble density of states in polar hosts. In gold‐bridged CMAs, this shift does not lead to a significant change in luminescence lifetime, thermal activation energy, reorganization energy, or intersystem crossing rate. These discoveries offer new insight into coupling between the singlet and triplet manifolds in CMA materials, revealing a dominant interaction between states of CT character. The same approach is employed using materials which have been chemically modified to alter the energy of their CT state directly, shifting the emission of sky‐blue chromophores into the practical blue range.     

Optimizing 100%‐renewable grids through shifting residential water‐heater load

A low‐carbon electricity supply for Australia was simulated, and the installed capacity of the electrical grid was optimized by shifting the electricity demand of residential electric water heaters (EWHs). The load‐shifting potential of Australia was estimated for each hour of the simulation period using a nationwide aggregate EWH load model on a 90 × 110 raster grid. The electricity demand of water heaters was shifted from periods of low renewable resource and high demand to periods of high renewable resource and low demand, enabling us to effectively reduce the installed capacity requirements of a 100%‐renewable electricity grid. It was found that by shifting the EWH load by just 1 hour, the electricity demand of Australia could be met using purely renewable electricity at an installed capacity of 145 GW with a capacity factor of 30%, an electricity spillage of 20%, and a generation cost of 15.2 ¢/kWh. A breakdown of the primary energy sources used in our scenario is as follows: 43% wind, 29% concentrated solar thermal power, and 20% utility photovoltaic. Sensitivity analysis suggested that further reduction in installed capacity is possible by increasing the load‐shifting duration as well as the volume and insulation level of the EWH tank.     

Woolrock—a material for technical use consisting of keratin

This article debates the production of mouldings made of keratin. It is demonstrated that the properties of keratin allow for being processed with heat and pressure to manufacture tough mouldings without chemical preprocessing of the used wool. This material thus has a high potential as a bioplastic, because it potentially can be used with conventional plastic manufacturing techniques. Additionally, it might also serve as an adhesive in various applications. The biobased material might become a sustainable source for mouldings.

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Novel oxidative in vitro metabolites of the mycotoxins alternariol and alternariol methyl ether

The Alternaria toxins alternariol (AOH; 3,7,9-trihydroxy-1-methyl-6H-benzo[c]chromen-6-one) and alternariol methyl ether (AME, 3,7-dihydroxy-9-methoxy-1-methyl-6H-benzo[c]chromen-6-one) are common contaminants of food and feed, but their oxidative metabolism in mammals is as yet unknown. We have therefore incubated AME and AOH with microsomes from rat, human, and porcine liver and analyzed the microsomal metabolites with HPLC and GC-MS/MS. Seven oxidative metabolites of AME and five of AOH were detected. Their chemical structures were derived from their mass spectra using deuterated trimethylsilyl (TMS) derivatives, and from the information obtained from enzymatic methylation. Several of the metabolites were identified by comparison with synthetic reference compounds. AME as well as AOH were monohydroxylated at each of the four possible aromatic carbon atoms and also at the methyl group. In addition, AME was demethylated to AOH and dihydroxylated to a small extent. As the four metabolites arising through aromatic hydroxylation of AME and AOH are either catechols or hydroquinones, the oxidative metabolism of these mycotoxins may be of toxicological significance.     

The Role of Oncostatin M and Its Receptor Complexes in Cardiomyocyte Protection,Regeneration, and Failure

Oncostatin M (OSM), a member of the interleukin-6 family, functions as a major mediator of cardiomyocyte remodeling under pathological conditions. Its involvement in a variety of human cardiac diseases such as aortic stenosis, myocardial infarction, myocarditis, cardiac sarcoidosis, and various cardiomyopathies make the OSM receptor (OSMR) signaling cascades a promising therapeutic target. However, the development of pharmacological treatment strategies is highly challenging for many reasons. In mouse models of heart disease, OSM elicits opposing effects via activation of the type II receptor complex (OSMR/gp130). Short-term activation of OSMR/gp130 protects the heart after acute injury, whereas chronic activation promotes the development of heart failure. Furthermore, OSM has the ability to integrate signals from unrelated receptors that enhance fetal remodeling (dedifferentiation) of adult cardiomyocytes. Because OSM strongly stimulates the production and secretion of extracellular proteins, it is likely to exert systemic effects, which in turn, could influence cardiac remodeling. Compared with the mouse, the complexity of OSM signaling is even greater in humans because this cytokine also activates the type I leukemia inhibitory factor receptor complex (LIFR/gp130). In this article, we provide an overview of OSM-induced cardiomyocyte remodeling and discuss the consequences of OSMR/gp130 and LIFR/gp130 activation under acute and chronic conditions.     

Enzymatic esterification of glycerol III. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols and 1 (3)-rac-monoacylglycerols derived from unsaturated fatty acids

Lipases that display high regioselectivities and broad substrate tolerance were used as catalysts for the efficient esterification of glycerol under the conditions of irreversible acyl transfer. A variety of unsaturated fatty acids, such as oleic, linoleic, erucic, ricinolic, hydroxystearic and coriolic acid, were used for this purpose in the form of their vinyl esters. Suitable biocatalysts were chosen on the basis of systematic screening experiments regarding their regioselectivities (RE) and substrate tolerances. Distinct differences were found and expressed in numerical RE values as a measure for differences of these biocatalysts as being specific, selective, and nonspecific. Based on these experiments, a variety of molecules were synthesized on a preparative scale (>150 mmol) in good yield (ca.85%) and with high regioisomerical purities (>95% RE).     

Fragment Mass Distribution of “Secondary Fragments”

An analysis of the secondary fragments emerging from a target plate has shown that their mass distribution fits excellently to a formula established earlier by the author. This applies equally well to the secondary fragments of an explosive-formed fragment from a multi-P warhead, to those from the warhead's structural casing. and even to the fragments from the target plate itself, as well as to the sum of all of these 3 types of fragements. The correlation coefficient for the two constant parameters governing this formula (namely, the scaling factor B and the form factor λ) is always better than 0.99, when an optimum total mass M_o is southt and inserted, and when the first, large fragements are not included in the consideration, which means when one or two measured points are negiected. For secondary fragements, the form factor λ in the mass distribution is close to 1/2 = 0.5, whereas for the natural fragments of HE projectiles it is in the order of 2/3. namely, from 0.6 to 0.8.