BINA

Aerogels offer a great platform for heterogeneous electrocatalysis owing to their high surface area and porosity. Atomically dispersed transition metal ions can be imbedded in these platforms at ultra‐high site density to make them catalytically active for various reactions. Herein, the synthesis of a new class of conjugated microporous organic aerogels that are used as covalent 3D frameworks for the electrocatalysis of oxygen reduction reaction (ORR) is reported. Modified aerogels functionalized with bipyridine ligands enable copper ion complexation in a single‐step synthesis. The aerogels’ structures are fully characterized using a wide array of spectroscopic and microscopic methods, and heat‐treated in order to make them electronically conductive. After heat treatment at 600 °C, the aerogels maintained their macrostructure and became active ORR catalysts in alkaline environment, showing high mass activity …

This paper is an initial proof of concept for an optical speckled-based method for the evaluation of facial nerve paralysis. Differences between the affected and the healthy sides of the face were measured in patients with Bell's palsy—a peripheral facial nerve paralysis. The patients’ faces were illuminated with two symmetrical spots on their nasolabial folds and the reflected speckle patterns were analyzed. Muscle activity was evaluated by muscle tone contraction-release motion inducing associated skin tilting movements. The skin movements were imaged with a defocused lens, which enables extraction of the speckle pattern's time changing trajectory. We found an asymmetry ratio expression that may be the key for the estimation of the degeneration level in Bell's palsy.

The Cu (II)‐diacetyl‐bis (N4‐methylthiosemicarbazone) complex (ATSM− Cu (II)) has been suggested as a promising positron emission tomography (PET) agent for hypoxia imaging. Several in‐vivo studies have shown its potential to detect hypoxic tumors. However, its uptake mechanism and its specificity to various cancer cell lines have been less studied. Herein, we tested ATSM− Cu (II) toxicity, uptake, and reduction, using four different cell types:(1) mouse breast cancer cells (DA‐3),(2) human embryonic kidney cells (HEK‐293),(3) breast cancer cells (MCF‐7), and (4) cervical cancer cells (Hela) under normoxic and hypoxic conditions. We showed that ATSM− Cu (II) is toxic to breast cancer cells under normoxic and hypoxic conditions; however, it is not toxic to normal HEK‐293 non‐cancer cells. We showed that the Cu (I) content in breast cancer cell after treatment with ATSM− Cu (II) under hypoxic conditions is …

Kaposi’s sarcoma-associated herpesvirus (KSHV) is a cancer-related herpesvirus. Like other herpesviruses, the KSHV icosahedral capsid includes a portal vertex, composed of 12 protein subunits encoded by open reading frame (ORF) 43, which enables packaging and release of the viral genome into the nucleus through the nuclear pore complex (NPC). Capsid vertex-specific component (CVSC) tegument proteins, which directly mediate docking at the NPCs, are organized on the capsid vertices and are enriched on the portal vertex. Whether and how the portal vertex is selected for docking at the NPC is unknown. Here, we investigated the docking of incoming ORF43-null KSHV capsids at the NPCs, and describe a significantly lower fraction of capsids attached to the nuclear envelope compared to wild-type (WT) capsids. Like WT capsids, nuclear envelope-associated ORF43-null capsids co-localized with different nucleoporins (Nups) and did not detach upon salt treatment. Inhibition of nuclear export did not alter WT capsid docking. As ORF43-null capsids exhibit lower extent of association with the NPCs, we conclude that although not essential, the portal has a role in mediating the interaction of the CVSC proteins with Nups, and suggest a model whereby WT capsids can dock at the nuclear envelope through a non-portal penton vertex, resulting in an infection ‘dead end’. View Full-Text

Coordinate‐transformation‐inspired optical devices have been mostly examined in the continuous‐wave regime: the performance of an invisibility cloak, which has been demonstrated for monochromatic excitation, is likely to deteriorate for short pulses. Here, pulse dynamics of flexural waves propagating in transformed plates is investigated. A practical realization of a waveshifter and a rotator for flexural waves based on the coordinate transformation method is proposed. Time‐resolved measurements reveal how the waveshifter deviates a short pulse from its initial trajectory, with no reflection at the bend and no spatial and temporal distortion of the pulse. Extending the strategy to cylindrical coordinates, a wave rotator is designed. It is demonstrated experimentally how a pulsed plane wave is twisted inside the rotator, while its wavefront is recovered behind the rotator and the pulse shape is preserved, with no extra …

The generation and amplification of photons by parametric down-conversion in quadratic nonlinear media is used as a source of entangled photons, squeezed light, and short optical pulses at difficult to access wavelengths. Optical nonlinearities are inherently weak, and therefore the pump energy required to produce sufficient gain for efficient down-conversion has been limited to energies in excess of nanojoules. Here we use dispersion-engineered nonlinear nanowaveguides driven by femtosecond pulses to demonstrate efficient down-conversion at the picojoule level; we observe parametric gains in excess of 70 decibels with pump pulse energies as little as 4 picojoules. When driven with pulse energies in excess of 10 picojoules these waveguides amplify vacuum fluctuations to 10\% of the pump power, and the generated bandwidth broadens to span an octave. These results represent a new class of parametric devices that combine sub-wavelength spatial confinement with femtosecond pulses to achieve efficient operation with remarkably low energy.

Adenosine-to-inosine editing is catalyzed by ADAR1 at thousands of sites transcriptome-wide. Despite intense interest in ADAR1 from physiological, bioengineering, and therapeutic perspectives, the rules of ADAR1 substrate selection are poorly understood. Here, we used large-scale systematic probing of ∼2,000 synthetic constructs to explore the structure and sequence context determining editability. We uncover two structural layers determining the formation and propagation of A-to-I editing, independent of sequence. First, editing is robustly induced at fixed intervals of 35 bp upstream and 30 bp downstream of structural disruptions. Second, editing is symmetrically introduced on opposite sites on a double-stranded structure. Our findings suggest a recursive model for RNA editing, whereby the structural alteration induced by the editing at one site iteratively gives rise to the formation of an additional editing site …

Trimetallic double hydroxide NiFeCoÀ OH is prepared by coprecipitation, from which three different catalysts are fabricated by different heat treatments, all at 350 C maximum temperature. Among the prepared catalysts, the one prepared at a heating and cooling rate of 2 C minÀ 1 in N2 atmosphere (designated NiFeCoÀ N2-2 C) displays the best catalytic properties after stability testing, exhibiting a high current density (9.06 mA cmÀ 2 at 320 mV), low Tafel slope (72.9 mVdecÀ 1), good stability (over 20 h), high turnover frequency (0.304 sÀ 1), and high mass activity (46.52 AgÀ 1 at 320 mV). Stability tests reveal that the hydroxide phase is less suitable for long-term use than catalysts with an oxide phase. Two causes are identified for the loss of stability in the hydroxide phase: a) Modeling of the distribution function of relaxation times (DFRT) reveals the increase in resistance contributed by various relaxation processes; b) density functional theory (DFT) surface energy calculations reveal that the higher surface energy of the hydroxide-phase catalyst impairs the stability. These findings represent a new strategy to optimize catalysts for water splitting.

We consider the extreme value statistics of N independent and identically distributed random variables, which is a classic problem in probability theory. When N→∞, fluctuations around the maximum of the variables are described by the Fisher-Tippett-Gnedenko theorem, which states that the distribution of maxima converges to one out of three limiting forms. Among these lies the Gumbel distribution, for which the convergence rate with N is of a logarithmic nature. Here, we present a theory that allows one to use the Gumbel limit to accurately approximate the exact extreme value distribution. We do so by representing the normalization sequences as power series, and by a transformation of the underlying distribution. We consider functional corrections to the Gumbel limit as well, showing they are obtainable via Taylor expansion. Our method improves the description of large deviations from the mean extreme value. It …

We formalize the concept of the modular energy operator within the Page and Wooters timeless framework. As a result, this operator is elevated to the same status as the more studied modular operators of position and momentum. In analogy with dynamical nonlocality in space associated with the modular momentum, we introduce and analyze the nonlocality in time associated with the modular energy operator. Some applications of our formalization are provided through illustrative examples.

Articular cartilage (AC) is a specialized connective tissue able to provide a low‐friction gliding surface supporting shock‐absorption, reducing stresses, and guaranteeing wear‐resistance thanks to its structure and mechanical and lubrication properties. Being an avascular tissue, AC has a limited ability to heal defects. Nowadays, conventional strategies show several limitations, which results in ineffective restoration of chondral defects. Several tissue engineering approaches have been proposed to restore the AC's native properties without reproducing its mechanical and lubrication properties yet. This work reports the fabrication of a bilayered structure made of gellan gum (GG) and poly (ethylene glycol) diacrylate (PEGDA), able to mimic the mechanical and lubrication features of both AC superficial and deep zones. Through appropriate combinations of GG and PEGDA, cartilage Young's modulus is effectively …

In a lithium–sulfur battery (LSB) discharge process, elemental sulfur is reduced to Li2S via a multi-step process. The soluble lithium-polysulfide (PS) (Li2Sn) intermediate species then diffuses through the electrolyte solution from the porous cathode to the lithium anode. These species react with the anode and form an interphase of insoluble lithium PS. This “shuttle” phenomenon is the main obstacle in the development of practical LSBs. The most previous reports dealt with LSBs focusing their attention on the cathode side, and the aspect of lithium reversibility influenced by the PS is not well quantified. In this paper, we designed an experimental protocol that allows us to control the exact amount of lithium in the cell and determine the influence of the different intermediate PS species on the reversibility of Li anode via spectroscopic, microscopic, and electrochemical techniques. We study the correlation between the …

In the search for replacement of the platinum‐based catalysts for fuel cells, MN4 molecular catalysts based on abundant transition metals play a crucial role in modeling and investigation of the influence of the environment near the active site in platinum‐group metal‐free (PGM‐free) oxygen reduction reaction (ORR) catalysts. To understand how the ORR activity of molecular catalysts can be controlled by the active site structure through modification by the pH and substituent functional groups, the change of the ORR onset potential and the electron number in a broad pH range was examined for three different metallocorroles. Experiments revealed a switch between two different ORR mechanisms and a change from 2e− to 4e− pathway in the pH range of 3.5‐6. This phenomenon was shown by density functional theory (DFT) calculations to be related to the protonation of the nitrogen atoms and carboxylic acid …

Measuring physical phenomena in an experimental system is commonly limited by the detector. When dealing with spatially defined behaviors, the critical parameter is the detector size. In this work, we examine near-infrared (NIR) measurements of turbid media using different size detectors at different positions. We examine cylindrical and semi-infinite scattering samples and measuring their intensity distribution. An apparent crossing point between samples with different scatterings was previously discovered and named the iso-pathlength point (IPL). Monte Carlo simulations show the expected changes due to an increase in detector size or similarly as the detector’s location is distanced from the turbid element. First, the simulations show that the intensity profile changes, as well as the apparent IPL. Next, we show that the average optical pathlength, and as a result, the differential pathlength factor, are mostly influenced by the detector size in the range close to the source. Experimental measurements using different size detectors at different locations validated the influence of these parameters on the intensity profiles and apparent IPL. These findings must be considered when assessing optical parameters based on multiple scattering models. In these cases, such as NIR assessment of tissue oxygenation, the size and location may cause false results of absorption or optical path.

Celiac disease (CD) is a complex immune-mediated chronic disease characterized by a consistent inflammation of the gastrointestinal tract induced by gluten intake in genetically predisposed individuals. Although initiated by the interaction between digestion-derived gliadin, a gluten component, peptides, and the intestinal epithelium, the disorder is highly complex and involving other components of the intestine, such as the immune system. Therefore, conventional model systems, mainly based on two-or three-dimension cell cultures and co-cultures, cannot fully recapitulate such a complex disease. The development of mouse models has facilitated the study of different interacting cell types involved in the disorder, together with the impact of environmental factors. However, such in vivo models are often expensive and time consuming. Here we propose an organ ex vivo culture (gut-ex-vivo system) based on small …

Assembly of materials into microstructures under laser guidance is attracting wide attention. The ability to pattern various materials and form 2D and 3D structures with micron/sub‐micron resolution and less energy and material waste compared with standard top‐down methods make laser‐based printing promising for many applications, for example medical devices, sensors, and microelectronics. Assembly from liquids provides a smaller feature size than powders and has advantages over other states of matter in terms of relatively simple setup, easy handling, and recycling. However, the simplicity of the setup conceals a variety of underlying mechanisms, which cannot be identified simply according to the starting or resulting materials. This progress report surveys the various mechanisms according to the source of the material—preformed or locally synthesized. Within each category, methods are defined …

Autonomous driving has recently gained lots of attention due to its disruptive potential and impact on the global economy; however, these high expectations are hindered by strict safety requirements for redundant sensing modalities that are each able to independently perform complex tasks to ensure reliable operation. At the core of an autonomous driving algorithmic stack is road segmentation, which is the basis for numerous planning and decision-making algorithms. Radar-based methods fail in many driving scenarios, mainly as various common road delimiters barely reflect radar signals, coupled with a lack of analytical models for road delimiters and the inherit limitations in radar angular resolution. Our approach is based on radar data in the form of a two-dimensional complex range-Doppler array as input into a deep neural network (DNN) that is trained to semantically segment the drivable area using weak …

Enzymes play pivotal roles in regulating and maintaining the normal functions of all living systems, and some of them are extensively employed for diagnosis and treatment of diverse diseases. More recently, several kinds of enzymes with unique catalytic activities have been found to be promising options to directly suppress tumor growth and/or augment the therapeutic efficacy of other treatments by modulating the hostile tumor microenvironment (TME), which is reported to negatively impair the therapeutic efficacy of different cancer treatments. In this review, first a summary is presented on the chemical approaches utilized for the construction of distinct enzyme nanoreactors with well‐retained catalytic performance and reduced immunogenicity. Then, the utilization of such enzyme nanoreactors in attenuating tumor hypoxia, modulating extracellular matrix, and amplifying tumor oxidative stress is discussed in depth …