Impact of Processing on Structural and Compositional Evolution in Mixed Metal Halide Perovskites during Film Formation

Understanding crystallization processes and their pathways in metal‐halide perovskites is of crucial importance as this strongly affects the film microstructure, its stability, and device performance. While many approaches are developed to control perovskite formation, the mechanisms of film formation are still poorly known. Using time‐resolved in situ grazing incidence wide‐angle X‐ray scattering, the film formation of perovskites is investigated with average stoichiometry Cs_0.15FA_0.85PbI₃, where FA is formamidinium, using the popular antisolvent dropping and gas jet treatments and this is contrasted with untreated films. i) The crystallization pathways during spin coating, ii) the subsequent postdeposition thermal annealing, and iii) crystallization during blade coating are studied. The findings reveal that the formation of a nonperovskite FAPbI₃ phase during spin coating is initially dominant regardless of the processing and that the processing treatment (e.g., antisolvent dropping, gas jet) has a significant impact on the as‐cast film structure and affects the phase evolution during subsequent thermal treatment. It is shown that blade coating can be used to overcome the nonperovskite phase formation via solvothermal direct crystallization of perovskite phase. This work shows how real‐time investigation of perovskite formation can help to establish processing–microstructure–functionality relationships.     

Optical reconstruction of high-speed surface dynamics in an uncontrollable environment

The ability to communicate with our voice can be regarded as the concatenation of the two processes "phonation" and "modulation." These take place in the larynx and palatal and oral region, respectively. During phonation the audible primary voice signal is created by mutual reaction of vocal folds with the exhaled air stream of the lungs. The underlying interactions of masses, fluids and acoustics have yet to be identified and understood. One part of the primary signal's acoustical source are vortex induced vibrations, as e.g., created by the Coand?effect in the air stream. The development of these vorteces is determined by the shape and 3-D movements of the vocal folds in the larynx. Current clinical in vivo research methods for vocal folds do not deliver data of satisfactory quality for fundamental research, e.g., an endoscope is limited to 2-D image information. Based hereupon, a few improved methods have been presented, however delivering only selective 3-D information, either for a single point or a line. This stands in contrast to the 3-D motions of the entire vocal fold surface. More complex imaging methods, such as MRI, do not deliver information in real-time. Thus, it is necessary to develop an easily applicable, more improved examination method, which allows for 3-D data of the vocal folds surfaces to be obtained. We present a method to calibrate a 3-D reconstruction setup including a laser projection system and a high-speed camera. The setup is designed with miniaturization and an in vivo application in mind. The laser projection system generates a divergent grid of 196 laser dots by diffraction gratings. It is calibrated with a planar calibration target through planar homography. In general, the setup allows to reconstruct the topology of a surface at high frame rates (up to 4000 frames per second) and in uncontrollable environments, as e.g., given by the lighting situation (little to no ambient light) and varying texture (e.g., varying grade of reflection) in the human larynx. In particular, this system measures the 3-D vocal fold surface dynamics during phonation. Applied to synthetic data, the calibration is shown to be robust (error approximately 0.5 μm) regarding noise and systematic errors. Experimental data gained with a linear z -stage proved that the system reconstructs the 3-D coordinates of points with an error at approximately 15 μm. The method was applied exemplarily to reconstruct porcine and artificial vocal folds' surfaces during phonation. Local differences such as asymmetry between left and right fold dynamics, as well as global parameters, such as opening and closing speed and maximum displacements, were identified and quantified.     

Artificial Microbial Arenas: Materials for Observing and Manipulating Microbial Consortia

From the smallest ecological niche to global scale, communities of microbial life present a major factor in system regulation and stability. As long as laboratory studies remain restricted to single or few species assemblies, however, very little is known about the interaction patterns and exogenous factors controlling the dynamics of natural microbial communities. In combination with microfluidic technologies, progress in the manufacture of functional and stimuli‐responsive materials makes artificial microbial arenas accessible. As habitats for natural or multispecies synthetic consortia, they are expected to not only enable detailed investigations, but also the training and the directed evolution of microbial communities in states of balance and disturbance, or under the effects of modulated stimuli and spontaneous response triggers. Here, a perspective on how materials research will play an essential role in generating answers to the most pertinent questions of microbial engineering is presented, and the concept of adaptive microbial arenas and possibilities for their construction from particulate microniches to 3D habitats is introduced. Materials as active and tunable components at the interface of living and nonliving matter offer exciting opportunities in this field. Beyond forming the physical horizon for microbial cultivates, they will enable dedicated intervention, training, and observation of microbial consortia.     

Inorganic-Based Printed Thermoelectric Materials and Devices

One of the simplest ways to generate electric power from waste heat is thermoelectric (TE) energy conversion. So far, most of the research on thermoelectrics has focused on inorganic bulk TE materials and their device applications. However, high production costs per power output and limited shape conformity hinder applications of state-of-the-art thermoelectric devices (TEDs). In recent years, printed thermoelectrics has emerged as an exciting pathway for their potential in the production of low-cost shape-conformable TEDs. Although several inorganic bulk TE materials with high performance are successfully developed, achieving high performance in inorganic-based printed TE materials is still a challenge. Nevertheless, significant progress has been made in printed thermoelectrics in recent years. In this review article, it is started with an introduction signifying the importance of printed thermoelectrics followed by a discussion of theoretical concepts of thermoelectricity, from fundamental transport phenomena to device efficiency. Afterward, the general process of inorganic TE ink formulation is summarized, and the current development of the inorganic and hybrid inks with the mention of their TE properties and their influencing factors is elaborated. In the end, TEDs with different architecture and geometries are highlighted by documenting their performance and fabrication techniques.     

Induction of Gushing with Recombinant Class II Hydrophobin FcHyd5p from Fusarium culmorum and the Impact of Hop Compounds on its Gushing Potential

Malt‐induced gushing is a problem that has been known for many years. Mechanisms and inducing agents are still not fully understood and identified. Hydrophobins produced by various filamentous fungi are currently under discussion as biological gushing‐inducing compounds. In the current study the class II hydrophobin FcHyd5p, from the cereal pathogen Fusarium culmorum, was employed in beer and other carbonated beverages for gushing experiments and the influence of hop compounds on gushing potential was examined. It was demonstrated that this protein strongly induces gushing in various carbonated beverages, including beer. It was further demonstrated that the resulting gushing volume is susceptible to certain hop compounds and can be decreased significantly by the addition of these substances.     

Highly efficient enzyme-functionalized porous zirconia microtubes for bacteria filtration

In contrast to polymer membranes, ceramic membranes offer considerable advantages for safe drinking water provision due to their excellent chemical, thermal, and mechanical endurance. In this study, porous ceramic microtubes made of yttria stabilized zirconia (YSZ) are presented, which are conditioned for bacteria filtration by immobilizing lysozyme as an antibacterial enzyme. In accordance with determined membrane pore sizes of the nonfunctionalized microtube of ≤200 nm, log reduction values (LRV) of nearly 3 (i.e., bacterial retention of 99.9%) were obtained for bacterial retention studies using gram-positive model bacterium Micrococcus luteus. Immobilization studies of lysozyme on the membrane surface reveal an up to six times higher lysozyme loading for the covalent immobilization route as compared to unspecific immobilization. Antibacterial activity of lysozyme-functionalized microtubes was assessed by qualitative agar plate test using Micrococcus luteus as substrate showing that both the unspecific and the covalent lysozyme immobilization enhance the microtubes' antibacterial properties. Quantification of the enzyme activity at flow conditions by photometric assays reveals that the enzyme activities of lysozyme-functionalized microtubes depend strongly on applied flow rates. Intracapillary feeding of bacteria solution and higher flow rates lead to reduced enzyme activities. In consideration of different applied flow rates in the range of 0.2-0.5 mL/min, the total lysozyme activity increases by a factor of 2 for the covalent immobilization route as compared to the unspecific binding. Lysozyme leaching experiments at flow conditions for 1 h show a significant higher amount of washed-out lysozyme (factor 1.7-3.4) for the unspecific immobilization route when compared to the covalent route where the initial level of antibacterial effectiveness could be achieved by reimmobilization with lysozyme. The presented platform is highly promising for sustainable bacteria filtration.     

Quantifizierende calciumspezies-analytik im wein zur frage der calciumstabilit?t

Zusammenfassung Die Calciumspezies-Stabilität als dekadischer Logarithmus der Komplex-Stabilitätskonstanten nach dem Massenwirkungsgesetz in Wein wird mit Hilfe der Direktpotentiometrie mit Ca-selektiver Elektrode (für die Calciumionenkonzentration) sowie der Photometrie (Ca-Gesamtgehalt) in 16 lager-stabilen Weinen (Ca-Gehalte zwischen 60 und 120 mg/l) mit 3,50±0,20 (Bereich 3,11–3,79) ermittelt. Durch Methodenvergleiche (Photometrie und AAS für Gesamtgehalte sowie Direktpotentiometrie und Ionenaustauschmethode für die Ionenkonzentration) wurden diese Ergebnisse abgesichert. Die Anwendung von Weinbehandlungsverfahren wie der Adsorption phenolischer Stoffe an Polyvinylpolypyrrolidin (PVPP) sowie der Ultrafiltration zur Abtrennung höhermolekularer Eiweißstoffe zeigte keine wesentlichen Veränderungen der Elementspezies-Stabilitäten. Bei einer Entsäuerung mit CaCO₃ oder nach der Doppelsalz-Entsäuerung wurde dagegen nicht nur ein Anstieg der Calciumgesamtgehalte auf 200 bis 535 mg/1 sondern auch eine deutliche Abnahme der Calciumspezies-Stabilität auf Werte von 2,2 bis 2,8 festgestellt. die nach dem Auskristallisieren von Calciumverbindungen nach einigen Wochen wieder Werte um 3 erreicht. Die Lagerstabilität eines Weines im Hinblick auf Calcium kann somit nach der Bestimmung der Calciumspezies-Stabilität beurteilt werden.

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Quantifying analysis of calcium species in wine from the point of view of calcium stability

Summary The stability of calcium species, expressed as the decadic logarithm of the complex stability constant after the chemical equilibrium had been established, was determined to be 3.50 ± 0.20 (range 3.11–3.79) by direct potentiometry with a calcium-selective electrode (for the calcium ion concentration) as well as photometry (total Ca content) in 16 storage-stable wines (Ca contents between 60 and 120 mg/1). By comparing the methods of photometry, AAS (for the total content) and direct potentiometry as well as ion-exchange method for ion concentrations, the results were verified. The treatment of the wine by the adsorption of phenolic substances on polyvinylpolypyrrolidine (PVPP) and by ultrafiltration for the separation of higher molecular proteins showed no significant changes in the stabilities of the calcium species. After deacidification with CaCO₃ or after salt deacidification had been performed twice, not only an increase in the total calcium content occured (200–535 mg/1), but there was also an evident decrease in the stabilities of the calcium species, which had values of 2.2–2.8 and reached values of 3 after crystallization of the calcium species. The storage stability of a wine, with respect to calcium, can be estimated after the determination of the stability of the calcium species.