Inherently chiral electrodes: the tool for chiral voltammetry

2,2′-Bis[2-(5,2′-bithienyl)]-3,3′-bithianaphthene oligomers are a model case of electroactive films endowed with “inherent chirality”, originating from a stereogenic element coinciding with the whole electroactive backbone, thus resulting in impressive manifestations. This study highlights their applicative potentialities as low-cost and easy-to-prepare artificial enantiopure electrode surfaces, which display an unprecedented ability to pronouncedly separate voltammetry peaks of enantiomers of quite different chiral probes of applicative interest, concurrently with linear dynamic ranges for peak currents, affording enantiomer excess determination. Thus inherently chiral enantiopure electrodes can indeed be regarded as a key to chiral voltammetry.     

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.     

Consistency issues of Lagrangian particle tracking applied to a spray jet in crossflow

Numerical simulations are performed for multiphase jets in crossflow. The flow solver uses an Eulerian/Lagrangian approach. Turbulence in the gas phase is modeled in the framework of large eddy simulation. The dispersed phase is handled using Lagrangian particle tracking. The model assumptions of solvers for Lagrangian particle tracking are critically assessed for typical flow conditions of spray jets in crossflow. The droplets are assumed to be spherical and isolated. It is shown that several model assumptions are apparently inconsistent in larger portions of the flow field. Firstly, average Weber numbers can be so large that the model assumption to regard droplets as spherical is questionable, not only near the nozzle, but also in the far-field. Secondly, the average droplet spacing can be so low that droplets directly interact with each other, again also in the far-field. Thirdly, the average Stokes numbers in the jet region can be so large that the phase coupling between the dispersed and continuous phase is weak. Some remedies to these deficiencies are proposed.     

An experimental and numerical investigation of different shear test configurations for sheet metal characterization

Simple shear tests are widely used for material characterization especially for sheet metals to achieve large deformations without plastic instability. This work describes three different shear tests for sheet metals in order to enhance the knowledge of the material behavior under shear conditions. The test setups are different in terms of the specimen geometry and the fixtures. A shear test setup as proposed by Miyauchi, according to the ASTM standard sample, as well as an in-plane torsion test are compared in this study. A detailed analysis of the experimental strain distribution measured by digital image correlation is discussed for each test. Finite element simulations are carried out to evaluate the effect of specimen geometries on the stress distributions in the shear zones. The experimental macroscopic flow stress vs. strain behavior shows no significant influence of the specimen geometry when similar strain measurements and evaluation schemes are used. Minor differences in terms of the stress distribution in the shear zone can be detected in the numerical results. This work attempts to give a unique overview and a detailed study of the most commonly used shear tests for sheet metal characterization. It also provides information on the applicability of each test for the observation of the material behavior under shear stress with a view to material modeling for finite element simulations.     

Investigation of azimuthal staging concepts in annular gas turbines

In this work, the influence of azimuthal staging concepts on the thermoacoustic behavior of annular combustion chambers is assessed theoretically and numerically. Staging is a well-known and effective method to abate thermoacoustic pulsations in combustion chambers. However, in the case of, for example, fuel staging the associated inhomogeneity of equivalence ratio may result in increased levels of NO_x emissions. In order to minimize this unwanted effect a staging concept is required in which the transfer functions of the burners are changed while affecting the equivalence ratio as little as possible. In order to achieve this goal, a theoretical framework for predicting the influence of staging concepts on pulsations has been developed. Both linear and nonlinear analytical approaches are presented and it is shown that the dynamics of azimuthal modes can be described by coupled Van der Pol oscillators. A criterion based on the thermoacoustic coupling strength and on the asymmetry degree provides the modal behavior in the annular combustor, i.e. standing or traveling waves. The model predictions have been verified by numerical simulations of a heavy-duty gas turbine using an in-house thermoacoustic network-modeling tool. The interaction between the heat release of the flame and the acoustic field was modeled using measured transfer functions and source terms. These numerical simulations confirmed the original theoretical considerations.     

Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO2 Exposure

Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d-states of FePc and the sp-band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The Fe^II ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO₂ dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO₂ at room temperature.     

Potential Use of Tea Tree Oil as a Disinfectant Agent against Coronaviruses: A Combined Experimental and Simulation Study

The COVID-19 pandemic has highlighted the relevance of proper disinfection procedures and renewed interest in developing novel disinfectant materials as a preventive strategy to limit SARS-CoV-2 contamination. Given its widely known antibacterial, antifungal, and antiviral properties, Melaleuca alternifolia essential oil, also named Tea tree oil (TTO), is recognized as a potential effective and safe natural disinfectant agent. In particular, the proposed antiviral activity of TTO involves the inhibition of viral entry and fusion, interfering with the structural dynamics of the membrane and with the protein envelope components. In this study, for the first time, we demonstrated the virucidal effects of TTO against the feline coronavirus (FCoVII) and the human coronavirus OC43 (HCoV-OC43), both used as surrogate models for SARS-CoV-2. Then, to atomistically uncover the possible effects exerted by TTO compounds on the outer surface of the SARS-CoV-2 virion, we performed Gaussian accelerated Molecular Dynamics simulations of a SARS-CoV-2 envelope portion, including a complete model of the Spike glycoprotein in the absence or presence of the three main TTO compounds (terpinen-4-ol, γ-terpinene, and 1,8-cineole). The obtained results allowed us to hypothesize the mechanism of action of TTO and its possible use as an anti-coronavirus disinfectant agent.     

External Micro-PIXE Measurements: Preliminary Results on Volcanic Rocks from Nyiragongo Volcano

The external microbeam facility at the 3 MV Tandetron accelerator of the LABEC Laboratory of INFN in Florence has been used to determine, by PIXE, major, minor and trace element abundances of minerals and groundmass in the lavas from the active Nyiragongo Volcano (Democratic Republic of Congo), which is well known for its lava lake intra-crateric activity [e.g. 1, 2]. During the last eruption of this volcano (January, 2002), two main flows entered the Goma town producing major devastation, forcing the rapid exodus of about 300,000 people and causing the death of 150 persons [3]. After this eruption, the interest of the scientific community on this volcanic area suddenly increased. In this respect, determination of major and trace element abundances in mineral phases and groundmass of lavas may allow to constrain the evolution of magma within the volcanic system from a quantitative view point, thus helping to better understand the way this volcano works. PIXE measurements have been performed in a two-detector setup that makes it possible to simultaneously detect and quantify all elements from Na to the heaviest ones; possible compositional zoning effects in the crystals can also be reliably measured thanks to the good space resolution of the microbeam facility (better than 10 μm) and to the possibility of performing one- and bi-dimensional scans over the areas of interest. Concentration maps of all elements can be obtained, both on-line and a posteriori: the data are collected with a list-mode acquisition system, which allows the distribution of any detected element to be reconstructed after completing the scan.     

Achromatic Number of K 5 × K n for Small n

The achromatic number of a graph G is the maximum number of colours in a proper vertex colouring of G such that for any two distinct colours there is an edge of G incident with vertices of those two colours. We determine the achromatic number of the Cartesian product of K ₅ and K _n for all n ≤ 24.