Some notes on extremal discriminant analysis

Classical discriminant analysis focusses on Gaussian and nonparametric models where in the second case the unknown densities are replaced by kernel densities based on the training sample. In the present article we assume that it suffices to base the classification on exceedances above higher thresholds, which can be interpreted as observations in a conditional framework. Therefore, the statistical modeling of truncated distributions is merely required. In this context, a nonparametric modeling is not adequate because the kernel method is inaccurate in the upper tail region. Yet one may deal with truncated parametric distributions like the Gaussian ones. Our primary aim is to replace truncated Gaussian distributions by appropriate generalized Pareto distributions and to explore properties and the relationship of discriminant functions in both models.     

Confocal scanning laser ophthalmoscopy improvement by use of Mueller-matrix polarimetry

A new technique for improving the signal-to-noise ratio and the contrast in images recorded with a confocal scanning laser system is presented. The method is based on the incorporation of a polarimeter into the setup. After the spatially resolved Mueller matrix of a sample was calculated, images for incident light with different states of polarization were reconstructed, and both the best and the worst images were computed. In both the microscope and the opthalmoscope modes, the best images are better than the originals. In contrast, the worst images are poorer. This technique may be useful in different fields such as confocal microscopy and retinal imaging.     

Agriculture crop residues as a source for the production of nanofibrillated cellulose with low energy demand

Nanofibrillated cellulose (NFC) from three agricultural crop (rice straw, corn and rapeseed stalk) residues was isolated with high-yield production using either high pressure homogenisation or a high speed blender. The fibres were extracted from the neat biomass via an NaClO₂/acetic acid and alkali pulping process. TEMPO-mediated oxidation pretreatment at pH 7 and 10 was accomplished to facilitate the release of the cellulose microfibrils. The fibrillation yield, transparency degree and morphological characteristics of the ensuing NFC were analysed using the centrifugation method, transmittance measurement and SEM observation. The energy consumption during the disintegration process was also accessed. It was shown that the mode of lignin removal and the fibre pretreatment notably affected the nanofibrillation efficiency and energy demand. A successful production of NFC with yield exceeding 90 %, using a simple Waring blender, was achieved when the NaClO₂/acetic acid delignification followed by a TEMPO-NaBr–NaClO oxidation at pH 10 was adopted.     

Strain‐Accelerated Formation of Chiral,Optically Active Buta‐1,3‐dienes

The formal [2+2] cycloaddition–retroelectrocyclization (CA–RE) reactions between tetracyanoethylene (TCNE) and strained, electron‐rich dibenzo‐fused cyclooctynes were studied. The effect of ring strain on the reaction kinetics was quantified, revealing that the rates of cycloaddition using strained, cyclic alkynes are up to 5500 times greater at 298 K than those of reactions using unstrained alkynes. Cyclobutene reaction intermediates, as well as buta‐1,3‐diene products, were isolated and their structures were studied crystallographically. Isolation of a rare example of a chiral buta‐1,3‐diene that is optically active and configurationally stable at room temperature is reported. Computational studies on the enantiomerization pathway of the buta‐1,3‐diene products showed that the eight‐membered ring inverts via a boat conformer in a ring‐flip mechanism. In agreement with computed values, experimentally measured activation barriers of racemization in these compounds were found to be up to 26 kcal mol^?1.     

Ionically Modified Gelatin Hydrogels Maintain Murine Myogenic Cell Viability and Fusion Capacity

For tissue engineering of skeletal muscles, there is a need for biomaterials which do not only allow cell attachment, proliferation, and differentiation, but also support the physiological conditions of the tissue. Next to the chemical nature and structure of the biomaterial, its response to the application of biophysical stimuli, such as mechanical deformation or application of electrical pulses, can impact in vitro tissue culture. In this study, gelatin methacryloyl (GelMA) is modified with hydrophilic 2-acryloxyethyltrimethylammonium chloride (AETA) and 3-sulfopropyl acrylate potassium (SPA) ionic comonomers to obtain a piezoionic hydrogel. Rheology, mass swelling, gel fraction, and mechanical characteristics are determined. The piezoionic properties of the SPA and AETA-modified GelMA are confirmed by a significant increase in ionic conductivity and an electrical response as a function of mechanical stress. Murine myoblasts display a viability of >95% after 1 week on the piezoionic hydrogels, confirming their biocompatibility. The GelMA modifications do not influence the fusion capacity of the seeded myoblasts or myotube width after myotube formation. These results describe a novel functionalization providing new possibilities to exploit piezo-effects in the tissue engineering field.     

Single-Nitrogen Atom Incorporation into B=B Bond via the N=N Bond Splitting of Diazo Compound and Diazirine

Triboraazabutenyne 3 is synthesized by the reaction of diboraazabutenyne 1 with aryl boron dibromide followed by the reduction. The ligand exchange to replace phosphine on the terminal sp² B atom with carbene furnishes 4 . ¹¹B NMR, solid-state structures, and computational studies disclose that 3 and 4 feature the extremely polarized B=B bond. 4 readily splits the N=N bond of both diazo compound and diazirine under ambient conditions, whereby one nitrogen atom is incorporated into the B=B moiety leading to a neutral diboraazaallene 6 . The mechanism of the reaction between 4 and diazo compound is extensively investigated by density functional theory (DFT) calculations, as well as the isolation of an intermediate.     

Comproportionation of CO2 and Cellulose to Formate Using a Floating Semiconductor-Enzyme Photoreforming Catalyst

Formate production via both CO₂ reduction and cellulose oxidation in a solar-driven process is achieved by a semi-artificial biohybrid photocatalyst consisting of immobilized formate dehydrogenase on titanium dioxide (TiO₂| FDH ) producing up to 1.16±0.04 mmol_formate g ⁻¹ in 24 hours at 30 °C and 101 kPa under anaerobic conditions. Isotopic labeling experiments with ¹³C-labeled substrates support the mechanism of stoichiometric formate formation through both redox half-reactions. TiO₂| FDH was further immobilized on hollow glass microspheres to perform more practical floating photoreforming allowing vertical solar light illumination with optimal light exposure of the photocatalyst to real sunlight. Enzymatic cellulose depolymerization coupled to the floating photoreforming catalyst generates 0.36±0.04 mmol_formate per m² irradiation area after 24 hours. This work demonstrates the synergistic solar-driven valorization of solid and gaseous waste streams using a biohybrid photoreforming catalyst in aqueous solution and will thus provide inspiration for the development of future semi-artificial waste-to-chemical conversion strategies.     

The Playground Shade Index: A New Design Metric for Measuring Shade and Seasonal Ultraviolet Protection Characteristics of Parks and Playgrounds

Current shading strategies used to protect outdoor playgrounds from harmful solar radiation include the placement of artificial cloth weaves or permanent roofing over a playground site, planting trees in proximity to playground equipment, and using vegetation or surface texture variations to cool playground surfaces. How and where an artificial shade structure is placed or a tree is planted to maximize the shade protection over specific playground areas, requires careful assessment of local seasonal sun exposure patterns. The Playground Shade Index (PSI) is introduced here as a design metric to enable shade and solar ultraviolet exposure patterns to be derived in an outdoor space using conventional aerial views of suburban park maps. The implementation of the PSI is demonstrated by incorporating a machine learning design tool to classify the position of trees from an aerial image, thus enabling the mapping of seasonal shade and ultraviolet exposure patterns within an existing 7180 m² parkland. This is achieved by modeling the relative position of the sun with respect to nearby buildings, shade structures, and the identified evergreen and deciduous tree species surrounding an outdoor playground.     

CO2 Aggregation on Monoethanolamine: Observations from Rotational Spectroscopy

The initial stages of the gas-phase nucleation between CO₂ and monoethanolamine were investigated via broadband rotational spectroscopy with the aid of extensive theoretical structure sampling. Sub-nanometer-scale aggregation patterns of monoethanolamine-(CO₂)_n, n=1–4, were identified. An interesting competition between the monoethanolamine intramolecular hydrogen bond and the intermolecular interactions between monoethanolamine and CO₂ upon cluster growth was discovered, revealing an intriguing CO₂ binding priority to the hydroxyl group over the amine group. These findings are in sharp contrast to the general results for aqueous solutions. In the quinary complex, a cap-like CO₂ tetramer was observed cooperatively surrounding the monoethanolamine. As the cluster approaches the critical size of new particle formation, the contribution of CO₂ self-assembly to the overall stability increases.