Toward a better understanding of multifunctional cement-based materials: The impact of graphite nanoplatelets (GNPs)

The impact of graphite nanoplatelets (GNPs) on the physical and mechanical properties of cementitious nanocomposites was investigated. A market-available premixed mortar was modified with 0.01% by weight of cement of commercial GNPs characterized by two distinctively different aspect ratios.The rheological behavior of the GNP-modified fresh admixtures was thoroughly evaluated. Hardened cementitious nanocomposites were investigated in terms of density, microstructure (Scanning Electron Microscopy, SEM and micro–Computed Tomography, μ-CT), mechanical properties (three-point bending and compression tests), and physical properties (electrochemical impedance spectroscopy, EIS and thermal conductivity measurements). At 28 days, all GNP-modified mortars showed about 12% increased density. Mortars reinforced with high aspect ratio GNPs exhibited the highest compressive and flexural strength: about 14% and 4% improvements compared to control sample, respectively. Conversely, low aspect ratio GNPs led to cementitious nanocomposites characterized by 36% decreased electrical resistivity combined with 60% increased thermal conductivity with respect to the control sample.     

Novel KCND3 Variant Underlying Nonprogressive Congenital Ataxia or SCA19/22 Disrupt KV4.3 Protein Expression and K+ Currents with Variable Effects on Channel Properties

KCND3 encodes the voltage-gated potassium channel K_V4.3 that is highly expressed in the cerebellum, where it regulates dendritic excitability and calcium influx. Loss-of-function K_V4.3 mutations have been associated with dominant spinocerebellar ataxia (SCA19/22). By targeted NGS sequencing, we identified two novel KCND3 missense variants of the K_V4.3 channel: p.S347W identified in a patient with adult-onset pure cerebellar syndrome and p.W359G detected in a child with congenital nonprogressive ataxia. Neuroimaging showed mild cerebellar atrophy in both patients. We performed a two-electrode voltage-clamp recording of K_V4.3 currents in Xenopus oocytes: both the p.G345V (previously reported in a SCA19/22 family) and p.S347W mutants exhibited reduced peak currents by 50%, while no K+ current was detectable for the p.W359G mutant. We assessed the effect of the mutations on channel gating by measuring steady-state voltage-dependent activation and inactivation properties: no significant alterations were detected in p.G345V and p.S347W disease-associated variants, compared to controls. K_V4.3 expression studies in HEK293T cells showed 53% (p.G345V), 45% (p.S347W) and 75% (p.W359G) reductions in mutant protein levels compared with the wildtype. The present study broadens the spectrum of the known phenotypes and identifies additional variants for KCND3-related disorders, outlining the importance of SCA gene screening in early-onset and congenital ataxia.     

NaWuReT-Workshop: Forschung in der Reaktionstechnik für und mit der Gesellschaft

In this article, the results of the NaWuReT (Early Career Reaction Engineers) workshop on the topic “Are we doing relevant science?” are presented. The topics “(In)surmountable hurdles for Citizen Scientists in reaction engineering?” and “Circular Economy in reaction engineering with/for society?” were discussed. Therefrom, a variety of ideas and suggestions were extracted.     

A Case of Double Standard: Sex Differences in Multiple Sclerosis Risk Factors

Multiple sclerosis is a complex, multifactorial, dysimmune disease prevalent in women. Its etiopathogenesis is extremely intricate, since each risk factor behaves as a variable that is interconnected with others. In order to understand these interactions, sex must be considered as a determining element, either in a protective or pathological sense, and not as one of many variables. In particular, sex seems to highly influence immune response at chromosomal, epigenetic, and hormonal levels. Environmental and genetic risk factors cannot be considered without sex, since sex-based immunological differences deeply affect disease onset, course, and prognosis. Understanding the mechanisms underlying sex-based differences is necessary in order to develop a more effective and personalized therapeutic approach.     

Chemical Characterization of Sorbitan Tri-Stearate Commercial Samples and Their Determination in Confectionery Fats by HPLC High-Resolution Mass Spectrometry

Nominal sorbitan tristearate (E492) commercial samples are widely used generally as emulsifiers and particularly as anti-bloom agents in confectionery products. In spite of this generalized use, their qualitative and quantitative evaluation is poorly documented in literature and the relative works go back to the last decades of last century. In the present work, a deep study by HPLC-High Resolution Mass Spectrometry of qualitative composition of five E492 commercial samples was made up showing a very complex pattern of stearic and palmitic acid esters with the sorbitol anhydrides, sorbitan, and isosorbide. A clear distinction of sorbitan mono-, di-, tri-, and tetra-esters, of sorbitol penta- and hexa-esters and isosorbide mono- and di-esters was achieved. Contemporarily, difference in the qualitative pattern between E492 commercial samples coming from different suppliers was established. As a consequence, quantitative evaluation can be reliably obtained by using as calibration standard the same E492 present in real samples. The accuracy and recovery of the method were determined allowing in this way a reliable application to commercial confectionery products. The detailed knowledge of STS composition may be of great help to orient the synthesis conditions in order to modulate its properties as a function of various experimental necessities.     

Methanol and proton transport through chitosan-phosphotungstic acid membranes for direct methanol fuel cell

Composite chitosan-phosphotungstic acid membranes were synthesized by ionotropic gelation. Their liquid uptake is higher for thin membranes (23 ± 2 μm), while it is lower (~70%) for thicker membranes (50-70 μm). Polarization curves recorded using single module fuel cell at 70°C allowed to estimate a peak power density of 60 mW cm⁻² by using 1 M as methanol and low Pt and Pt/Ru loadings (0.5 and 3 mg cm⁻²) at the cathode and at the anode, respectively. Electrochemical impedance spectroscopy was used to estimate the membrane conductivity and to model the electrochemical behavior of methanol electrooxidation inside the fuel cell revealing a two-step mechanism mainly responsible of overall kinetic losses. Transport of methanol inside the membrane was studied by potentiostatic measurements, allowing to estimate a methanol diffusivity of 3.6 × 10⁻⁶ cm² s⁻¹.     

4D Printing of a Bioinspired Microneedle Array with Backward‐Facing Barbs for Enhanced Tissue Adhesion

Microneedle (MN), a miniaturized needle with a length‐scale of hundreds of micrometers, has received a great deal of attention because of its minimally invasive, pain‐free, and easy‐to‐use nature. However, a major challenge for controlled long‐term drug delivery or biosensing using MN is its low tissue adhesion. Although microscopic structures with high tissue adhesion are found from living creatures in nature (e.g., microhooks of parasites, barbed stingers of honeybees, quills of porcupines), creating MNs with such complex microscopic features is still challenging with traditional fabrication methods. Here, a MN with bioinspired backward‐facing curved barbs for enhanced tissue adhesion, manufactured by a digital light processing 3D printing technique, is presented. Backward‐facing barbs on a MN are created by desolvation‐induced deformation utilizing cross‐linking density gradient in a photocurable polymer. Barb thickness and bending curvature are controlled by printing parameters and material composition. It is demonstrated that tissue adhesion of a backward‐facing barbed MN is 18 times stronger than that of barbless MN. Also demonstrated is sustained drug release with barbed MNs in tissue. Improved tissue adhesion of the bioinspired MN allows for more stable and robust performance for drug delivery, biofluid collection, and biosensing.     

Improved Biocompatibility of Amino‐Functionalized Graphene Oxide in Caenorhabditis elegans

Graphene oxide (GO) holds high promise for diagnostic and therapeutic applications in nanomedicine but reportedly displays immunotoxicity, underlining the need for developing functionalized GO with improved biocompatibility. This study describes adverse effects of GO and amino‐functionalized GO (GONH₂) during Caenorhabditis elegans development and ageing upon acute or chronic exposure. Chronic GO treatment throughout the C. elegans development causes decreased fecundity and a reduction of animal size, while acute treatment does not lead to any measurable physiological decline. However, RNA‐Sequencing data reveal that acute GO exposure induces innate immune gene expression. The p38 MAP kinase, PMK‐1, which is a well‐established master regulator of innate immunity, protects C. elegans from chronic GO toxicity, as pmk‐1 mutants show reduced tissue‐functionality and facultative vivipary. In a direct comparison, GONH₂ exposure does not cause detrimental effects in the wild type or in pmk‐1 mutants, and the innate immune response is considerably less pronounced. This work establishes enhanced biocompatibility of amino‐functionalized GO in a whole‐organism, emphasizing its potential as a biomedical nanomaterial.     

Unconventional Nanofabrication for Supramolecular Electronics

The scientific effort toward achieving a full control over the correlation between structure and function in organic and polymer electronics has prompted the use of supramolecular interactions to drive the formation of highly ordered functional assemblies, which have been integrated into real devices. In the resulting field of supramolecular electronics, self‐assembly of organic semiconducting materials constitutes a powerful tool to generate low‐dimensional and crystalline functional architectures. These include 1D nanostructures (nanoribbons, nanotubes, and nanowires) and 2D molecular crystals with tuneable and unique optical, electronic, and mechanical properties. Optimizing the (opto)electronic properties of organic semiconducting materials is imperative to harness such supramolecular structures as active components for supramolecular electronics. However, their integration in real devices currently represents a significant challenge to the advancement of (opto)electronics. Here, an overview of the unconventional nanofabrication techniques and device configurations to enable supramolecular electronics to become a real technology is provided. A particular focus is put on how single and multiple supramolecular fibers and gels as well as supramolecularly engineered 2D materials can be integrated into novel vertical or horizontal junctions to realize flexible and high‐density multifunctional transistors, photodetectors, and memristors, exhibiting a set of new properties and excelling in their performances.     

Ejection chain moves for automatic neighborhood synthesis in constrained cardinality‐minimization problems

In this paper, we deal with the problem of automatically synthesizing “good” neighborhoods for a specific class of problems, namely constrained cardinality‐minimization problems. Exploiting the peculiarity of the objective function of such problems, we develop automatic ejection chain moves that define neighborhood structures to be explored with a black‐box solver. In particular, starting from a formulation of a cardinality‐minimization problem and a feasible solution, our procedure automatically detects the “entities” involved in the problem and learns the strength of the relationships among them. This information is then used to define the characteristics of our moves that consist in ejecting one entity at a time from the solution. If one of such moves results in an infeasible solution, then feasibility is recovered by performing an additional step based on the solution of an auxiliary problem. The computational results show that, when assessed on four well‐known constrained cardinality‐minimization problems, our approach outperforms both a black‐box mixed integer programming solver and a state‐of‐the‐art model‐based neighborhood search procedure with respect to both solution quality and computing times.