High transmission 3D printed flex‐PCB‐based ion funnel

In this study a novel fabrication method for a radio frequency (RF) ion funnel is presented. RF ion funnels are important devices for focusing ion clouds at low vacuum conditions for mass spectrometry or deposition‐related applications. Typically, ion funnels are constructed of stainless steel plate ring electrodes with a decreasing diameter where RF and direct current potentials are applied to the electrodes to focus the ion cloud. The presented novel design is based on a flexible circuit board that serves both as the signal distribution circuit and as the electrodes of the ion funnel. The flexible circuit board is rolled into a 3D printed scaffold to create a funnel shape with ring electrodes formed by the copper electrodes of the flexible circuit board. The design is characterized in direct comparison with a conventional steel‐plate electrode design. The discussed results show that the new funnel has similar performance to the conventionally designed funnel despite much lower manufacturing costs. Copyright © 2015 John Wiley & Sons, Ltd.     

A Highly‐Ordered 3D Covalent Fullerene Framework

A highly‐ordered 3D covalent fullerene framework is presented with a structure based on octahedrally functionalized fullerene building blocks in which every fullerene is separated from the next by six functional groups and whose mesoporosity is controlled by cooperative self‐assembly with a liquid‐crystalline block copolymer. The new fullerene‐framework material was obtained in the form of supported films by spin coating the synthesis solution directly on glass or silicon substrates, followed by a heat treatment. The fullerene building blocks coassemble with a liquid‐crystalline block copolymer to produce a highly ordered covalent fullerene framework with orthorhombic Fmmm symmetry, accessible 7.5 nm pores, and high surface area, as revealed by gas adsorption, NMR spectroscopy, small‐angle X‐ray scattering (SAXS), and TEM. We also note that the 3D covalent fullerene framework exhibits a dielectric constant significantly lower than that of the nonporous precursor material.     

Tunable Porosities and Shapes of Fullerene‐Like Spheres

The formation of reversible switchable nanostructures monitored by solution and solid‐state methods is still a challenge in supramolecular chemistry. By a comprehensive solid state and solution study we demonstrate the potential of the fivefold symmetrical building block of pentaphosphaferrocene in combination with Cu^I halides to switch between spheres of different porosity and shape. With increasing amount of CuX, the structures of the formed supramolecules change from incomplete to complete spherically shaped fullerene‐like assemblies possessing an I_h‐C₈₀ topology at one side and to a tetrahedral‐structured aggregate at the other. In the solid state, the formed nano‐sized aggregates reach an outer diameter of 3.14 and 3.56 nm, respectively. This feature is used to reversibly encapsulate and release guest molecules in solution.     

DNA‐Based Oligochromophores as Light‐Harvesting Systems

The chromophores ethynyl pyrene as blue, ethynyl perylene as green and ethynyl Nile red as red emitter were conjugated to the 5‐position of 2′‐deoxyuridine via an acetylene bridge. Using phosphoramidite chemistry on solid phase labelled DNA duplexes were prepared that bear single chromophore modifications, and binary and ternary combinations of these chromophore modifications. The steady‐state and time‐resolved fluorescence spectra of all three chromophores were studied in these modified DNA duplexes. An energy‐transfer cascade occurs from ethynyl pyrene over ethynyl perylene to ethynyl Nile red and subsequently an electron‐transfer cascade in the opposite direction (from ethynyl Nile red to ethynyl perylene or ethynyl pyrene, but not from ethynyl perylene to ethynyl pyrene). The electron‐transfer processes finally provide charge separation. The efficiencies by these energy and electron‐transfer processes can be tuned by the distances between the chromophores and the sequences. Most importantly, excitation at any wavelength between 350 and 700 nm finally leads to charge separated states which make these DNA samples promising candidates for light‐harvesting systems.     

Influence of the Base on Pd@MIL‐101‐NH2(Cr) as Catalyst for the Suzuki–Miyaura Cross‐Coupling Reaction

The chemical stability of metal–organic frameworks (MOFs) is a major factor preventing their use in industrial processes. Herein, it is shown that judicious choice of the base for the Suzuki–Miyaura cross‐coupling reaction can avoid decomposition of the MOF catalyst Pd@MIL‐101‐NH₂(Cr). Four bases were compared for the reaction: K₂CO₃, KF, Cs₂CO₃ and CsF. The carbonates were the most active and achieved excellent yields in shorter reaction times than the fluorides. However, powder XRD and N₂ sorption measurements showed that the MOF catalyst was degraded when carbonates were used but remained crystalline and porous with the fluorides. XANES measurements revealed that the trimeric chromium cluster of Pd@MIL‐101‐NH₂(Cr) is still present in the degraded MOF. In addition, the different countercations of the base significantly affected the catalytic activity of the material. TEM revealed that after several catalytic runs many of the Pd nanoparticles (NPs) had migrated to the external surface of the MOF particles and formed larger aggregates. The Pd NPs were larger after catalysis with caesium bases compared to potassium bases.     

Application of Crude Pomace Powder of Chokeberry,Bilberry, and Elderberry as a Coloring Foodstuff

Berry pomace, rich in polyphenols, especially anthocyanins, accumulates during the production of red juices. Pomace from chokeberry (Aronia melanocarpa Michx.), bilberry (Vaccinium myrtillus L.), and elderberry (Sambucus nigra L.) represent good sources of coloring foodstuffs. Pomace powders (PP) were prepared by milling the seedless fractions of the three dried berry pomaces (50 °C, 8 h). Techno-functional properties of the powders such as particle size distribution, bulk density, sedimentation velocity, and swelling capacity were determined to evaluate the powders for possible food applications. Total anthocyanin content was quantified by UHPLC-DAD before and during a storage experiment to monitor the degradation of anthocyanins in the PP and in a yogurt model application. The high content of phenolic compounds and the still intact cell structure ensured high stability of anthocyanins over 28 days of storage. In the model application, color saturation was stable over the whole storage time of 14 days. Regarding the techno-functional properties, only a few differences between the three PP were observed. The particle size of elderberry PP was larger, resulting in lowest bulk density (0.45 g/mL), high cold-water solubility (16.42%), and a swelling capacity of 10.16 mL/g dw. Sedimentation velocity of the three PP was fast (0.02 mL/min) due to cluster formation of the particles caused by electrostatic and hydrophobic properties. Compared to other high-intensity coloring foodstuffs, the use of PP, showing acceptable color stability with potential health-promoting effects, represents a wide applicability in different food applications and especially in products with a longer shelf-life.     

Combustion behavior of ammonia blended with diethyl ether

Ammonia (NH₃) is recognized as a carbon-free hydrogen-carrier fuel with a high content of hydrogen atoms per unit volume. Recently, ammonia has received increasing attention as a promising alternative fuel for internal combustion engine and gas turbine applications. However, the viability of ammonia fueling future combustion devices has several barriers to overcome. To overcome the challenge of its low reactivity, it is proposed to blend it with a high-reactivity fuel. In this work, we have investigated the combustion characteristics of ammonia/diethyl ether (NH₃/DEE) blends using a rapid compression machine (RCM) and a constant volume spherical reactor (CVSR). Ignition delay times (IDTs) of NH₃/DEE blends were measured using the RCM over a temperature range of 620 to 942 K, pressures near 20 and 40 bar, equivalence ratios (Φ) of 1 and 0.5, and a range of mole fractions of DEE, χ_DEE, from 0.05 to 0.2 (DEE/NH₃ = 5 – 20%). Laminar burning velocities of NH₃/DEE premixed flames were measured using the CVSR at 298 K, 1 bar, Φ of 0.9 to 1.3, and χ_DEE from 0.1 to 0.4. Our results indicate that DEE promotes the reactivity of fuel blends resulting in significant shortening of the ignition delay times of ammonia under RCM conditions. IDTs expectedly exhibited strong dependence on pressure and equivalence ratio for a given blend. Laminar burning velocity was found to increase with increasing fraction of DEE. The burnt gas Markstein length increased with equivalence ratio for χ_DEE = 0.1 as seen in NH₃-air flames, while the opposite evolution of Markstein length was observed with Φ for 0.1 < χ_DEE ≤ 0.4, as observed in isooctane-air flames. A detailed chemical kinetics model was assembled to analyze and understand the combustion characteristics of NH₃/DEE blends.     

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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