Mixing and detonation structure in a rotating detonation engine with an axial air inlet

High-fidelity simulations of an experimental rotating detonation engine with an axial air inlet were conducted. The system operated with hydrogen as fuel at globally stoichiometric conditions. Instantaneous data showed that the detonation front is highly corrugated, and is considerably weaker than an ideal Chapman–Jouguet wave. Regions of deflagration are present ahead of the wave, caused by mixing with product gases from the previous cycle, as well as the injector recovery process. It is found that as the post-detonation high pressure flow expands, the injectors recover unsteadily, leading to a transient mixing process ahead of the next cycle. The resulting flow structure not only promotes mixing between product and reactant gases, but also increases likelihood of autoignition. These results show that the detonation process is very sensitive to injector design and the transient behavior during the detonation cycle. Phase-averaged statistics and conditionally averaged data are used to understand the overall reaction structure. Comparisons with available experimental data on this configuration show remarkable good agreement of the predicted reacting flow structure.     

Autoignition in stratified mixtures for pressure gain combustion

The reliable generation of quasi-homogeneous autoignition inside a combustor fed by a continuous air flow would represent a milestone in realizing pressure gain combustion in gas turbines. In this work, the ignition distribution inside a stratified fuel–air mixture is analyzed. The ability of precise and reproducible injection of a desired fuel profile inside a convecting air flow is verified by applying tunable diode laser absorption spectroscopy in non-reacting measurements. High-speed, static pressure sensors and ionization probes allow for simultaneous detection of the flame and pressure rise at several axial positions in reactive measurements with dimethyl ether as fuel. A second, exchangeable combustion tube enables optical observation of OH* intensity in combination with pressure measurements. Experiments with three arbitrary fuel profiles show a set of ignition distributions that vary in shape, homogeneity, and the number of simultaneous autoignition events. Although the measurements show notable variation, a significant and reproducible influence of the fuel injection on the ignition distribution is observed. Results show that uniform autoignition leads to a coupling of the reaction front with the pressure rise and, therefore, induces a greater aerodynamic constraint than non-uniform ignition distributions, which are dominated by propagating deflagration fronts.     

Identification and Partial Structural Characterization of Mass Isolated Valsartan and Its Metabolite with Messenger Tagging Vibrational Spectroscopy

Recent advances in the coupling of vibrational spectroscopy with mass spectrometry create new opportunities for the structural characterization of metabolites with great sensitivity. Previous studies have demonstrated this scheme on 300 K ions using very high power free electron lasers in the fingerprint region of the infrared. Here we extend the scope of this approach to a single investigator scale as well as extend the spectral range to include the OH stretching fundamentals. This is accomplished by detecting the IR absorptions in a linear action regime by photodissociation of weakly bound N₂ molecules, which are attached to the target ions in a cryogenically cooled, rf ion trap. We consider the specific case of the widely used drug Valsartan and two isomeric forms of its metabolite. Advantages and challenges of the cold ion approach are discussed, including disentangling the role of conformers and the strategic choices involved in the selection of the charging mechanism that optimize spectral differentiation among candidate structural isomers. In this case, the Na⁺ complexes are observed to yield sharp resonances in the high frequency NH and OH stretching regions, which can be used to easily differentiate between two isomers of the metabolite.

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Enantioselective Organophotocatalytic Telescoped Synthesis of a Chiral Privileged Active Pharmaceutical Ingredient

The continuous flow, enantioselective, organophotoredox catalytic asymmetric alkylation of aldehydes was studied, by using a homemade, custom-designed photoreactor for reactions under cryogenic conditions. Going from microfluidic conditions up to a 10 mL mesofluidic reactor, an increase of productivity by almost 18000 % compared to the batch reaction was demonstrated. Finally, for the first time, a stereoselective photoredox organocatalytic continuous flow reaction in a fully telescoped process for an active pharmaceutical ingredient (API)synthesis was successfully achieved. The final process consists of four units of operation: visible light-driven asymmetric catalytic benzylation under continuous flow, inline continuous work-up, neutralisation and a final oxidative amidation step afforded the pharmaceutically active molecule in 95 % e.e.     

Direct C−H Trifluoromethylation of (Hetero)Arenes in Water Enabled by Organic Photoredox-Active Amphiphilic Nanoparticles

Photoredox-catalyzed chemical conversions are predominantly operated in organic media to ensure good compatibility between substrates and catalysts. Yet, when conducted in aqueous media, they are an attractive, mild, and green way to introduce functional groups into organic molecules. We here show that trifluoromethyl groups can be readily installed into a broad range of organic compounds by using water as the reaction medium and light as the energy source. To bypass solubility obstacles, we developed robust water-soluble polymeric nanoparticles that accommodate reagents and photocatalysts within their hydrophobic interior under high local concentrations. By taking advantage of the high excited state reduction potential of N-phenylphenothiazine (PTH) through UV light illumination, the direct C−H trifluoromethylation of a wide array of small organic molecules is achieved selectively with high substrate conversion. Key to our approach is slowing down the production of CF₃ radicals during the chemical process by reducing the catalyst loading as well as the light intensity, thereby improving effectiveness and selectivity of this aqueous photocatalytic method. Furthermore, the catalyst system shows excellent recyclability and can be fueled by sunlight. The method we propose here is versatile, widely applicable, energy efficient, and attractive for late-stage introduction of trifluoromethyl groups into biologically active molecules.     

Enhancement of Sodium Ion Battery Performance Enabled by Oxygen Vacancies

The utilization of oxygen vacancies (OVs) in sodium ion batteries (SIBs) is expected to enhance performance, but as yet it has rarely been reported. Taking the MoO_3?x nanosheet anode as an example, for the first time we demonstrate the benefits of OVs on SIB performance. Moreover, the benefits at deep‐discharge conditions can be further promoted by an ultrathin Al₂O₃ coating. A series of measurements show that the OVs increase the electric conductivity and Na‐ion diffusion coefficient, and the promotion from ultrathin coating lies in the effective reduction of cycling‐induced solid‐electrolyte interphase. The coated nanosheets exhibited high reversible capacity and great rate capability with the capacities of 283.9 (50 mA g^?1) and 179.3 mAh g^?1 (1 A g^?1) after 100 cycles. This work may not only arouse future attention on OVs for sodium energy storage, but also open up new possibilities for designing strategies to utilize defects in other energy storage systems.     

Improved efficiency in GaAs solar cells by 1D and 2D nanopatterns fabricated by laser interference lithography

We demonstrate an improvement in efficiency of GaAs solar cells using front surface texturing with dielectric 1D and 2D nanopatterns obtained by a low cost laser interference lithography technique. The strong light scattering by the surface dielectric nanopatterns effectively increases the optical path of the incident light in the absorber layers resulting in an efficiency increase up to 23.5% compared to that of the reference solar cell. The observed efficiency improvement in the studied solar cells shows the potential use of low cost photoresist as an antireflection coating material and further application of other robust dielectric materials as texturing layer.     

EPR Spectra of Spin-labeled Fatty Acids in Detergent Solutions: “Immobilized Species” in the Absence of Protein

Electron paramagnetic resonance spectra of 5-doxyl-stearic acid, 3-(2-Dodecyl-1-oxyl-5,5-dimethylpyrrolidin-2-yl)propanoic acid radical (4-proxyl-palmitic acid) and of 3-(1-Oxyl-2,5-dimethyl-5-dodecylpyrrolidine-2-yl)propanoic acid radical (4-azetoxyl-stearic acid) in lipid micelles of nonaethyleneglycol-monododecyl ether (C₁₂E₉) and pentaethyleneglycol-monooctyl ether (C₈E₅) can reveal immobilized components typical of spin-labeled protein-bound fatty acids as well as phospholipids. The occurrence of such species depends on the detergent, the relative orientation of the nitroxide group with respect to the longitudinal axis and the molecular structure of the fatty acid as well as on polarity and ionic strength of the aqueous phase. Whereas 5-doxyl-stearic acid and 4-proxyl-palmitic acid exhibited these highly immobilized components in C₁₂E₉ micelles but not in C₈E₅, only a single relatively mobile component was observed with 4-azetoxyl-stearic acid in both detergents. The immobilized component is lost by the addition of isopropanol but not as much by ethanol and also when distilled water is substituted for the buffer.