Crossing the Border: From Keto- to Imine Reduction in Short-Chain Dehydrogenases/Reductases

The family of NAD(P)H-dependent short-chain dehydrogenases/reductases (SDRs) comprises numerous biocatalysts capable of C=O or C=C reduction. The highly homologous noroxomaritidine reductase (NR) from Narcissus sp. aff. pseudonarcissus and Zt_SDR from Zephyranthes treatiae, however, are SDRs with an extended imine substrate scope. Comparison with a similar SDR from Asparagus officinalis (Ao_SDR) exhibiting keto-reducing activity, yet negligible imine-reducing capability, and mining the Short-Chain Dehydrogenase/Reductase Engineering Database indicated that NR and Zt_SDR possess a unique active-site composition among SDRs. Adapting the active site of Ao_SDR accordingly improved its imine-reducing capability. By applying the same strategy, an unrelated SDR from Methylobacterium sp. 77 (M77_SDR) with distinct keto-reducing activity was engineered into a promiscuous enzyme with imine-reducing activity, thereby confirming that the ability to reduce imines can be rationally introduced into members of the “classical” SDR enzyme family. Thus, members of the SDR family could be a promising starting point for protein approaches to generate new imine-reducing enzymes.     

Two-step pyrolytic engineering to form porous nitrogen-rich carbons with a 3D network structure for Zn-air battery oxygen reduction electrocatalysis

It is of great urgency to design inexpensive and high-performance oxygen reduction reaction (ORR) electrocatalysts derived from biowastes as substitutes for Pt-based materials in electrochemical energy-conversion devices. Here we propose a strategy to synthesize three-dimensional (3D) porous nitrogen-doped network carbons to catalyze the ORR from two-step pyrolysis engineering of biowaste scale combined with the use of a ZnCl₂ activator and a FeCl₂ promotor. Electrochemical tests show that the synthesized network carbons have exhibited comparable ORR catalytic activity with a half-wave potential (~0.85 V vs. RHE) and outstanding cyclical stability in comparison to the Pt/C catalyst. Beyond that, a high electron transfer number (~3.8) and a low peroxide yield (<7.6%) can be obtained, indicating a four-electron reaction pathway. The maximum power density is ~68 mW cm^?2, but continuous discharge curves (at a constant potential of ~1.30 V) for 12 h are not obviously declined in Zn-air battery tests using synthesized network carbons as the cathodic catalyst. The formation of 3D porous structures with high BET surface area can effectively expose the surface catalytic sites and promote mass transportation to boost the ORR activity. This work may open a new idea to prepare porous carbon-based catalysts for some important reactions in new energy devices.     

Abrasive waterjet micro-machining of channels in metals: Comparison between machining in air and submerged in water

Abrasive water jet technology can be used for micro-milling using recently developed miniaturized nozzles. Abrasive water jet (AWJ) machining is often used with both the nozzle tip and workpiece submerged in water to reduce noise and contain debris. This paper compares the performance of submerged and unsubmerged abrasive water jet micro-milling of channels in 316L stainless steel and 6061-T6 aluminum at various nozzle angles and standoff distances. The effect of submergence on the diameter and effective footprint of AWJ erosion footprints was measured and compared. It was found that the centerline erosion rate decreased with channel depth due to the spreading of the jet as the effective standoff distance increased, and because of the growing effect of stagnation as the channel became deeper. The erosive jet spread over a larger effective footprint in air than in water, since particles on the jet periphery were slowed much more quickly in water due to increased drag. As a result, the width of a channel machined in air was wider than that in water. Moreover, it was observed that the instantaneous erosion rate decreased with channel depth, and that this decrease was a function only of the channel cross-sectional geometry, being independent of the type of metal, the jet angle, the standoff distance, and regardless of whether the jet was submerged or in air, in either the forward or backward directions. It is shown that submerged AWJM results in narrower features than those produced while machining in air, without a decrease in centerline etch rate.     

Correlation between instrumental texture and colour quality attributes with sensory analysis of selected cheeses as affected by fat contents

This study evaluated several physical and sensory parameters of different types of cheese available in the Polish market. The measurements of textural properties were conducted in an Instron universal testing machine, while the colour properties of cheeses were measured using a Minolta chromameter. The chemical composition was determined by means of the near‐infrared spectroscopy (NIRs). Moreover, a trained sensory panel was invited to assess the cheese texture‐related properties. Generally, cheeses with reduced fat content were characterised by higher hardness, adhesiveness, cohesiveness and elasticity. Texture‐related parameters of cheese with canola oil were comparable to that of most of full‐fat cheeses. The correlation analysis between physical and sensory attributes related to cheese textural properties indicated the potential applications of TPA, shear and penetration tests (r = 0.766, r = 0.75 and r = 0.765, respectively) for the evaluation of sensory properties related to the hardness. Meanwhile, the elasticity of cheese obtained from sensory evaluation was strongly correlated with the elasticity determined from the shear test (r = 0.722) and moderately correlated with the elasticity from penetration test (r = 0.588), indicating a need to refine the method of penetration test. In addition, cheeses exhibited higher meltability during convection heating at 230 °C than microwave heating. The values of meltability for cheese with reduced fat content were lower than those of full‐fat cheese.     

Predicting the thermodynamics of aluminum dross denitrification of flue gas

Existing alumina extraction and material production methods result in the formation of harmful ammonia gas or ammonia water originating from aluminum nitride (AlN) in dross. Therefore, in this study, aluminum dross was used as a denitration reagent to eliminate nitrogen oxides in flue gas and AlN in dross. Based on the proposed scheme, thermodynamic calculations were performed to investigate the denitrification effect and reduction of aluminum dross in flue gas. The results show that equilibrium concentrations of NO, NO₂, and HF in the flue gas were influenced mainly by temperature; their concentrations increased with an increase in the temperature, reaching 4.4 × 10⁻²⁰, 1.7 × 10⁻³⁸, and 7.0 × 10⁻⁸ g/m³, respectively, at 923 K. The Gibbs free energy corresponding to the reaction of CO₂ with Al/AlN in aluminum dross was −377/–120 kJ/mol. HF, originating from the reaction of NaF and water vapor, maintained an extremely low concentration of 6.99 × 10⁻⁸ g/m³ at 923 K. These results indicate that aluminum dross processing may clean the flue gas and increase the calorific value while eliminating the hazards of AlN. The results obtained herein will provide theoretical guidance toward new avenues of aluminum dross utilization.     

One-Pot Methods for the Protection and Assembly of Sugars

In recent years, there has been rapid expansion of glycan synthesis, fueled by the recognition that the structural complexity of sugars translates to a myriad of biological functions. Such chemical syntheses involve many challenges, mostly due to the regio- and stereochemical aspects of glycosidic bond formation. One-pot strategies were developed to assist in attaining faster and more economical access to the glycan constructs. In this front, achievements in protecting group manipulation, glycosylation, and combinations of these have been reported. Protecting group manipulations in one pot take advantage of the reaction compatibility of commonly used transformations, many of which occur in high regioselectivity. Sequential glycosylations, on the other hand, rely on leaving group orthogonalities and reactivity tuning, as well as the preactivation technique. Altogether, these approaches offer attractive means to the much needed glycan structures and, consequently, help usher in advances in glycoscience.     

Experimental and numerical study on compressive performance of perforated brick masonry after fire exposure

This paper discusses the compressive performance of perforated brick masonry after fire exposure. Compressive strength tests of the mortar, clay perforated brick, and perforated brick masonry specimens were performed in accordance with ISO834 fire tests of different durations. The temperature distribution of the masonry materials and specimens was simulated using the finite element software ABAQUS, with the thermal parameters of masonry materials recommended by European standard Eurocode 6 and related literature. The compressive strength reduction factors of mortar and clay perforated brick exposed to different fire durations were calculated via the layered method suggested by European standard Eurocode 1. In addition, the compressive strength reduction factors after cooldown were obtained from the experimental data of the masonry materials, and by considering further reductions in the compressive strength after cooling from high temperatures. Experimental data of the masonry specimens were compared with the numerical results obtained using the reduction factors proposed in this work. The comparison revealed an overall acceptable approximation. Thus, the method presented in this paper can be used to evaluate the residual capacity of masonry structures after fire.     

Graph-based video fingerprinting using double optimal projection

A double optimal projection method that involves projections for intra-cluster and inter-cluster dimensionality reduction are proposed for video fingerprinting. The video is initially set as a graph with frames as its vertices in a high-dimensional space. A similarity measure that can compute the weights of the edges is then proposed. Subsequently, the video frames are partitioned into different clusters based on the graph model. Double optimal projection is used to explore the optimal mapping points in a low-dimensional space to reduce the video dimensions. The statistics and geometrical fingerprints are generated to determine whether a query video is copied from one of the videos in the database. During matching, the video can be roughly matched by utilizing the statistics fingerprint. Further matching is thereafter performed in the corresponding group using geometrical fingerprints. Experimental results show the good performance of the proposed video fingerprinting method in robustness and discrimination.     

Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.