BINA

New naphthocorrole ligands, display both the cavity size of corroles and the dianionic character of porphyrins. Nonaromatic and yet flaunting deceptively porphyrin-like optical spectra, they are readily accessible via a simple protocol.

The development of vacuum‐deposited perovskite materials and devices is partially slowed down by the minor research effort in this direction, due to the high cost of the required research tools. But there is also another factor, thermal co‐deposition in high vacuum involves the simultaneous sublimation of several precursors with an overall deposition rate in the range of few Å s−1. This leads to a deposition time of hours with only a single set of process parameters per batch, hence to a long timeframe to optimize even a single perovskite composition. Here we report the combinatorial vacuum deposition of wide bandgap perovskites using 4 sources and a non‐rotating sample holder. By using small pixel substrates, more than 100 solar cells can be produced with different perovskite absorbers in a single deposition run. The materials are characterized by spatially resolved methods, including optical, morphological …

Dynamics and Fluctuations in Biomedical Photonics XX Page 1 PROGRESS IN BIOMEDICAL OPTICS AND IMAGING Vol. 24 No. 27 Volume 12378 Proceedings of SPIE, 1605-7422, V. 12378 SPIE is an international society advancing an interdisciplinary approach to the science and application of light. Dynamics and Fluctuations in Biomedical Photonics XX Valery V. Tuchin Martin J. Leahy Ruikang K. Wang Zeev Zalevsky Editors 29–30 January 2023 San Francisco, California, United States Sponsored and Published by SPIE Dynamics and Fluctuations in Biomedical Photonics XX, edited by Valery V. Tuchin, Martin J. Leahy, Ruikang K. Wang, Zeev Zalevsky, Proc. of SPIE Vol. 12378, 1237801 · © 2023 SPIE · 1605-7422 · doi: 10.1117/12.2676834 Proc. of SPIE Vol. 12378 1237801-1 Page 2 The papers in this volume were part of the technical conference cited on the cover and title page. Papers were selected and …

Recovery from damage in materials helps extend their useful lifetime and of devices that contain them. Given that the photodamages in HaP materials and based devices are shown to recover, the question arises if this also applies to mechanical damages, especially those that can occur at the nanometer scale, relevant also in view of efforts to develop flexible HaP‐based devices. Here, this question is addressed by poking HaP single crystal surfaces with an atomic force microscope (AFM) tip under both ultra‐high vacuum (UHV) and variably controlled ambient water vapor pressure conditions. Sequential in situ AFM scanning allowed real‐time imaging of the morphological changes at the damaged sites. Using methylammonium (MA) and cesium (Cs) variants for A‐site cations in lead bromide perovskites, the experiments show that nanomechanical damages on methylammonium lead bromide (MAPbBr3) crystals …

Platinum group metal‐free catalysts have been considered the most promising alternative for platinum‐based catalysts for the oxygen reduction reaction in fuel cells. Despite the significant advancement made in activity, their viability as fuel cell catalysts is still questionable due to their low durability. So far, deciphering the degradation mechanisms of this class of catalysts has been hampered by their undefined structure. Herein, we used a molecular model catalyst, iron‐phthalocyanine, featuring Fe−N4 active sites with resemblance to those in the more active Fe−N−C catalysts, and studied their degradation mechanisms. Based on X‐ray photoelectron spectroscopy and the electrochemical measurements, three main demetallation processes were identified: at potentials higher than 0.65 V vs. RHE, where the metal center is Fe3+, an electrochemical oxidation of the ligand ring is occurring, between 0.6 and 0.2 V …

Oxygen reduction reaction (ORR) is considered the bottleneck reaction in fuel cells. Its sluggish kinetics requires the use of scarce and expensive platinum group metal (PGM) catalysts. Significant efforts have been invested in trying to find a PGM‐free catalyst to replace Pt for this reaction or reduce its loadings. One interesting family of materials that has shown great promise in doing so is aerogels, which are based on covalent frameworks. The aerogels’ high surface area and porosity enable good mass transport and high catalyst utilization that is expected to lower PGM loadings or replacing them completely. This review summarizes recent research in this field, introducing methods of using aerogels as cathodes for ORR, from carbon to metal aerogels. The catalytic sites vary from nanoparticles to atomically dispersed metal ions embedded in carbon aerogels that form all‐in‐one platform which can serve as both …

Climate change calls for a change in the way we use and produce energy, and carbon-free has become the future direction of energy production and utilization. To obtain this, we must rely on sustainable energy sources such as wind and sun, but their intermittence limits the production of clean energy to only a few hours a day. To overcome this issue, energy storage and production technologies must be developed. Although several technologies have been proposed, the only viable scheme that could allow short-to-long-term storage and efficient energy transportation at-scale is the hydrogen economy, which relies on three pillars of technology: electrolyzers, hydrogen storage and fuel cells. In recent years, there have been rapid technological advances in hydrogen production, new hydrogen storage materials, and high-performance hydrogen fuel cells, etc. However, there are still numerous technological difficulties …

Gene editing promises the ultimate cure for genetic diseases by directly correcting disease-causing variants. However, the first clinical trials have chased the “low hanging fruit” using editing strategies that rely on gene disruption by introducing double-strand DNA breaks that lead to insertions and deletions (indels) by the NHEJ pathway. Since NHEJ is constitutively active throughout the cell cycle and the default DNA repair pathway, this is by far the most efficient type of conventional gene editing as opposed to homology-directed repair (HDR). HDR relies on delivery of an exogenous repair template and this pathway is active only in the S and G2 phases of the cell cycle. These two parameters constitute challenges in clinical use of HDR since exogenous DNA is toxic in most therapeutically relevant cell types and since the inherent competition between NHEJ and HDR can be a bottleneck. However, HDR benefits …

Although non-alkaline rechargeable Zn-air batteries (RZABs) are promising for energy storage, their chemistry is still underdeveloped and unclear. It was suggested that using Zn(OAc)2 or Zn(OTf)2 aqueous solutions as electrolytes enables reversible, corrosion-free charge-discharge proccesses, but anodic stability of carbon in these cells has remained poorly studied. We report that CO2 evolution is manifested during oxygen evolution reaction in non-alkaline RZABs, which is associated with corrosion of carbon scaffolds. This corrosion is observed for different electrolyte compositions, such as Zn(OAc)2, ZnSO4 and Zn(OTf)2 solutions of various concentrations. The corrosion rate decreases when the overpotentials during oxygen evolution reaction are lower. This study underlines the importance of addressing the anodic instability of carbon in non-alkaline RZABs.

Chaos, namely exponential sensitivity to initial conditions, is generally considered a nuisance, inasmuch as it prevents long‐term predictions in physical systems. Here, an easily accessible approach to undo deterministic chaos and tailor ray trajectories in arbitrary 2D optical billiards by introducing spatially varying refractive index therein is presented. A new refractive index landscape is obtained by a conformal mapping, which makes the trajectories of the chaotic billiard fully predictable and the billiard fully integrable. Moreover, trajectory rectification can be pushed a step further by relating chaotic billiards with non‐Euclidean geometries. Two examples are illustrated by projecting billiards built on a sphere as well as the deformed spacetime outside a Schwarzschild black hole, which respectively lead to all periodic orbits and spiraling trajectories remaining away from the boundaries of the transformed 2D billiards …

The development of bioinspired catalysts for oxygen reduction reaction is one of the most prominent pathways in the search for active materials to replace Pt-based catalysts in fuel cells. Herein, we report innovative bioinspired catalysts using a directed synthetic pathway to create adjacent Cu and Fe sites. This catalyst is composed of a covalent 3D framework in an aerogel form. Aerogels are high surface area and porous hierarchical structures that can allow the formation of ultrahigh active site density and optimized mass transport of reactants and products to and from the catalytic sites. The aerogel-based catalyst exhibits high performance in a half-cell in 0.1 M KOH, with an onset potential of 0.94 V vs RHE and half-wave potential of E1/2 = 0.80 V vs RHE, high selectivity toward the four-electron reduction of oxygen to hydroxide anions, and high durability. These results are well-translated to the anion exchange …

The realization of lithium-oxygen (Li-O2) batteries has been impeded by parasitic reactions that cause cell component degradation, often accompanied by the release of CO2 gas during oxidation reactions. The use of halide-based redox mediators (RMs) like LiBr and LiI has been proposed as a strategy to reduce overpotentials during oxygen evolution reactions and thus suppress the subsequent evolution of CO2. However, there is a scarcity of research examining the effectiveness of these RMs in the direct mitigation of parasitic reactions. In this study, we investigated the evolution of CO2 during the oxidation processes using an online electrochemical mass spectrometer. The results show that cells without RMs exhibited high overpotentials and significant CO2 evolution from the first charging cycle. In contrast, the addition of 50mM LiI to the electrolyte resulted in a delay in CO2 evolution, observed only after several …

Metamaterials and plasmonic structures made from aluminum (Al) have attracted significant interest due to their low cost, long-term stability, and the relative abundance of aluminum compared to the rare metals. Also, aluminum displays distinct dielectric properties allowing for the excitation of surface plasmons in the ultraviolet region with minimal non-radiative losses. Despite these clear advantages, most of the research has been focused on either gold or silver, probably due to difficulties in forming smooth thin films of aluminum. In the present work, we detect and characterize second harmonic generation (SHG) in the optical regime, emanating from triangular hole arrays milled into thin aluminum films in reflection mode, at normal incidence. We report intense nonlinear responses, year-long stability, and overall superior performances with respect to gold and silver. The robustness of the Al structures and high …

A sustainable future based on hydrogen fuel rests its faith on the rapid advancement of non-precious metal catalysts for the oxygen evolution reaction (OER). We demonstrate the efficient utilisation in the analysis of a large compositional space of binary NiFe and ternary NiFeV alloys for OER using a combinatorial method. We fabricated a gradient library of these multi metal alloys using physical vapor deposition and characterised them using high-throughput techniques. The electrocatalytic OER activity was studied using an automated electrochemical scanning droplet cell (SDC) set up designed in our lab. From the overpotential (@10mA/cm2) heatmaps of the libraries, the compositional regime of interest is funnelled down to 10-15% of Fe and 85-90 % of Ni for the NiFe alloy and 1-3% V, 10-15% Fe, and 80-90% Ni for the NiFeV alloy with their overpotential values falling between 320 – 330 mV. Due to its oxidation …

Lithiated oxides like Li[NixCoyMnz]O2 (x+y+z=1) with high nickel content (x≥0.8) can possess high specific capacity ≥ 200 mAhg-1 and have attracted extensive attention as perspective cathode materials for advanced lithium-ion batteries. In this work, we synthesized LiNi0.9Co0.1O2 (NC90) materials and studied their structural characteristics, electrochemical performance, and thermal behavior in Li-cells. We developed modified cationic-doped NC90 samples with greatly improved properties due to doping with Mo6+ and B3+ and dual doping via simultaneous modification with these dopants. The main results of the current study are significantly higher capacity retention, greatly reduced voltage hysteresis, and considerably decreased charge-transfer resistance of the Mo and Mo-B doped electrodes compared to the undoped ones upon prolonged cycling. We also revealed remarkable microstructural stability of …

The ban on many chemical pesticides has facilitated interest in discovery and application of bacteria (termed biocontrol agents) that antagonize soilborne plant pathogens. These bacteria protect plants from pathogens through a variety mechanisms that include niche exclusion (Wang et al., 2021), metabolic competition (Spadaro et al., 2010), production of siderophores (Yu et al., 2010; Li et al., 2014), secretion of chitinases that target the chitin components of fungal cell walls (Veliz et al., 2017), antibacterial and antifungal compounds (Raaijmakers et al., 2002; Ongena and Jacques, 2008), and induction of plant resistance (Pieterse et al., 2014). Secondary metabolites (SM),

Correction for ‘Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries’ by Maximilian Mellin et al., Mater. Adv., 2023, 4, 3746–3758, https://doi.org/10.1039/D3MA00236E.

The discovery of the Ti3C2Tx compounds (MXenes) a decade ago opened new research directions and valuable opportunities for high‐rate energy storage applications. The unique ability of the MXenes to host various mono‐ and multivalent cations and their high stability in different electrolyte environments including aqueous, organic, and ionic liquid solutions, promoted the rapid development of advanced MXene‐based electrodes for a large variety of applications. Unlike the vast majority of typical intercalation compounds, the electrochemical performance of MXene electrodes is strongly influenced by the presence of co‐inserted solvent molecules, which cannot be detected by conventional current/potential electrochemical measurements. Furthermore, the electrochemical insertion of ions into MXene interspaces results in strong coupling with the intercalation‐induced structural, dimensional, and viscoelastic …

Detection of target molecules, such as proteins, antibodies, or specific DNA sequences, is critical in medical laboratory science. Commonly used assays rely on tagging the target molecules with fluorescent probes. These are then fed to high-sensitivity detection systems. Such systems typically consist of a photodetector or camera and use time-resolved measurements that require sophisticated and expensive optics. Magnetic modulation biosensing (MMB) is a novel, fast, and sensitive detection technology that has been used successfully to detect viruses such as Zika and SARS-CoV-2. While this powerful tool is known for its high analytical and clinical sensitivity, the current signal-processing method for detecting the target molecule and estimating its dose is based on time-resolved measurements only. To improve the MMB-system performance, we propose here a novel signal processing algorithm that uses both temporally and spatially resolved measurements. We show that this combination significantly improves the sensitivity of the MMB-based assay. To evaluate the new method statistically, we performed multiple dose responses of Human Interleukin 9 (IL -8) on different days. Compared to standard time-resolved methods, the new algorithm provides a 2-3 fold improvement in detection limit and a 25% improvement in quantitative resolution.

Regarding energy density, safety, cost, and sustainability rechargeable magnesium batteries are a very promising next-generation energy storage technology. However, for a successful commercialization of Mg batteries there are still some challenges to overcome. Generally, the high charge density of the bivalent cation causes strong coulomb interactions with anions and solvent molecules. Therefore, energetic barriers for desolvation and solid-state diffusion are usually very high, which can have a crucial impact on the battery performance. Former can significantly hinder the electron-transfer reaction,[1] whereas latter makes the choice of suitable cathode materials very challenging. For instance, it is wellknown that the morphology of an intercalation material can strongly influence the battery performance and smaller particles as well as thinner electrodes are common strategies for avoiding adverse effects of transport limitations. Moreover, the presence of chlorides can influence the intercalation process.[2] Up to date Chevrel phase (CP) Mo6S8 is considered as a benchmark intercalation cathode. In our contribution we carefully study this model system of a magnesium-ion battery to get a better understanding of how to overcome undesired limitations. Therefore, we present a newly-developed continuum model, which is able to describe the complex intercalation process of magnesium cations into a CP cathode (Fig. 1). The model considers not only the different thermodynamics and kinetics of the two intercalation sites of Mo6S8 and their interplay, but also the impact of the desolvation on the electrochemical reactions and possible ion …

Oil‐in‐water emulsion droplets spontaneously adopt, below some temperature Td, counterintuitive faceted and complex non‐spherical shapes while remaining liquid. This transition is driven by a crystalline monolayer formed at the droplets' surface. Here, we show that ppm‐level doping of the droplet's bulk by long‐chain alcohols allows tuning Td by >50 °C, implying formation of drastically different interfacial structures. It finds that “magic” alcohol chain lengths maximize Td. This is shown to arise from self‐assembly of mixed alcohol:alkane interfacial structures of stacked alkane layers, co‐crystallized with hydrogen‐bonded alcohol dimers. It accounts for these structures theoretically and resolve them by direct cryogenic transmission electron microscopy (cryoTEM), confirming the proposed structures. The discovered tunability of key properties of commonly‐used emulsions by minute concentrations of specific bulk …