Hot stamping dies include cooling channels to treat the formed sheet. The optimum cooling channels of dies & molds should adapt to the shape and surface of the dies, so that a homogeneous temperature distribution and cooling are guaranteed. Nevertheless, cooling ducts are conventionally manufactured by deep drilling, attaining straight channels unable to follow the geometry of the tool. Laser Metal Deposition (LMD) is an additive manufacturing technique capable to fabricate nearly free-form integrated cooling channels and therefore shape the so-called conformal cooling. The present work investigates the design and manufacturing of conformal cooling ducts, which are additively built up on hot work steel and then milled in order to attain the final part. Their mechanical performance and heat transfer capability has been evaluated, both experimentally and by means of thermal simulation. Finally, conformal cooling conduits are evaluated and compared to traditional straight channels. The results show that LMD is a proper technology for the generation of cooling ducts, opening the possibility to produce new geometries on dies & molds and, therefore, new products.

A series of novel chiral nonmetallocene pincer-type rare earth metal dialkyl complexes bearing the chiral monoanionic tridentate C2-symmetric 1,3-bis(oxazolinymethylidene)isoindoline (BOXMI) ligand (BOXMI)Ln(CH2SiMe3)2 1-3 (1, Ln = Sc, yield = 57%; 2, Ln = Lu, yield = 55%; 3, Ln = Y, yield = 62%) have been prepared in moderate yields via the acid-base reaction between the BOXMI ligand and rare earth metal tri(trimethylsilylmethyl) complexes. The X-ray diffractions show that both of the complexes 1 and 2 contain one Boxmi ligand and two trimethylsilylmethyl ligands, adopting a distorted-trigonal-bipyramidal configuration. In the presence of cocatalyst such as borate and AlR3, these complexes 1-3 exhibit high activities up to 6.8 × 104 (g of polymer)/(molLn h) and high cis-1,4-selectivities up to 97%) in the polymerization of isoprene in toluene, yielding the cis-1,4-polyisoprenes with high molecular weights (Mn up to 710000 g/mol) and bimodal molecular weight distributions (Mw/Mn = 2.0-4.5).

In this work, we investigated the effects of heat treatment on the microstructure, hydrogen storage characteristics and corrosion rate of a Ti₃₄V₄₀Cr₂₄Fe₂ alloy. The arc melted alloy was divided into three samples, two of which were separately quartz-sealed under vacuum and heated to 1000 °C for 1 h; one of these samples was quenched and the other furnace cooled to ambient temperature. The crystal structures of the samples were studied via X-ray diffractometry and scanning electron microscopy. Absorption/desorption characteristics were investigated using a Sievert apparatus. Potentiostat corrosion tests on the alloys were performed using an AutoLab^® corrosion test apparatus and electrochemical cell. All samples exhibited a mixture of body-center-cubic (BCC) and Laves phase structures. The corrosion rate, maximum absorption, and useful capacities increased after both heat treatments. The annealed sample had the highest absorption and reversible capacity. The plateau pressure of the as-cast alloy increased after quenching. The corrosion rate increased from 0.0004 mm/y in as-cast sample to 0.0009 mm/y after annealing and 0.0017 mm/y after quenching, due to a decrease in the Cr-content of the C14 phase.

The mechanistic pathway of TEMPO/I₂-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 is investigated in this study. Based on our direct empirical experiments, three key intermediates (the aminium radical cation 3, the α-aminoalkyl radical 4, and the iminium 5), four kind reactive species (radical TEMPO, cationic TEMPO, TEMPO-I and iodo radical) and three kind pathways (1. SET/PCET mechanism, 2. HAT/1,6-H transfer mechanism, 3. Ionic mechanism) were assumed. Under the assumption, nine free energy diagrams are acquired through DFT calculation. From the comparison of the solution phase free energy, some possibility can be excluded and then the chosen plausible mechanisms are concretized with the more stable intermediate 7.

The study reveals correlations between the parameters of ions and their HOMO and LUMO orbital energy level values. In particular, it demonstrates a clear correlation for the ion adsorption parameters on model electrodes: the aluminum oxide (0001) surface, graphene and Au (111) surface. Correlations are also observed for the parameters of ion binding to water and dimethyl carbonate molecules, which are often used as solvents. In addition, the dipole moment, polarizability and solvation energy of ions are well correlated with the values of the molecular orbital energies, and for anions a dependence on the oxidation potential is observed. The obtained descriptors make it possible to select ions with desired values for a specific problem. As an illustrative example, in this work we consider the problem of displacement of water molecules from the inner electric double layer by ions, which is one of the factors increasing the potential window in electrolytes of aqueous batteries. This approach can be applied in the rapidly developing field of aqueous electrolytes for battery or supercapacitor design, catalysis control through surface composition variations, as well as in studies of heavy metal ion binding to sorption materials.

Water pollution is the main problem in the current scenario which is being faced by mankind due to the industrial and commercial effects. Industrial effluents contain heavy metals and inorganic ions like nitrates and phosphate ions. These ions are being included in waterways through industrial runoff. When the concentration of these hazardous pollutants increases in aquatic flora and fauna causes severe health problems. So remediation of these toxicants from water reserves is of chief importance. Conventional processes along with modern processes are being used for the treatment of industrial wastes. Photo-degradation is a modern method used for the degradation of inorganic ions due to its environmentally friendly nature and cost-effectiveness. In a recent study Aluminum oxide (Al2O3) nanoparticles were synthesized via a green approach at different pH by using Cymbopogan citratus (lemongrass) plant extract and these nanoparticles were used for the removal of inorganic ions from wastewater. The nanoparticles of different pH showed different % degradation of the inorganic ions in acidic medium removal of inorganic waste was less, in basic media % degradation was more as compared to acidic media but maximum % degradation was observed in neutral media like that average % degradation 91% and 81% was observed for nitrate and phosphate ions. The maximum absorbance occurred at 212nm and Al2O3 nanoparticles showed absorbance from 210nm-217nm. The R2 values of pseudo1st, 2nd, and BMG models were 0.956, 0.837, 0.7007 0.95, 0.896, and 0.756 for the nitrate and phosphate ions. Characterizations of synthesized particles were investigated by using UV-visible spectroscopy and other analytical methods like X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The statistical analyses were done using Simple Linear regression (SLR).

A bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative (PN-DOPO) in combination with aluminum phosphates coated sepiolite (Sep@AlPO4) was used to improve the flame retardancy, thermal stability and mechanical properties of poly (ethylene oxide) (PEO)/poly (butylene adipate-co-terephthalate) (PBAT) blends. The synergistic effects of PN-DOPO and Sep@AlPO4 on the fire resistance, thermal decomposition behavior and mechanical properties of PEO/PBAT composites were investigated systematically. The results indicated that 5 wt % Sep@AlPO4 combined with 10 wt% PN-DOPO into PEO/PBAT achieved a V-1 rating in UL-94 test and the LOI value increased to 23.7%, meanwhile, the peak-heat release rate (p-HRR), av-HRR and total heat release (THR) values of PEO/PBAT/PN10%/Sep5% composites decreased by 35.6%, 11.0% and 23.0% compared with those of PEO/PBAT, respectively. The thermogravimetric analysis (TGA) results confirmed that PN-DOPO/Sep@AlPO4 could enhance the initial thermal stability and char yield of PEO/PBAT matrix, and TGA/Fourier transform infrared spectrometry (TGA-FTIR) results revealed that the composites exhibited the absorption peaks of phosphorous-containing groups and an increase in gas-phase volatiles during the thermal decomposition process. The digital photographs and morphological structures of char residues demonstrated that PN-DOPO and Sep@AlPO4 mixtures benefited to the formation of a more continuous and dense carbon layer on the composites surface during combustion. Rheological behavior revealed that a higher storage modulus, loss modulus and complex viscosity of PEO/PBAT/PN-DOPO/Sep@AlPO4 composites could also promote the cross-linking structure during burning. Furthermore, the PEO/PBAT/PN-DOPO/Sep@AlPO4 composites exhibited excellent mechanical properties in terms of elongation at break and flexural performance than the PEO/PBAT system. All the results demonstrated that PEO/PBAT system modified by the combination of PN-DOPO and Sep@AlPO4 not only exhibited excellent synergistic effect on the flame retardance, but also had good improvement on thermal stability and mechanical properties, indicating the potential application in areas requiring fire safety.

Nanofiber (NF) products exhibit outstanding performances in the materials science, textile, and medical fields, which cannot be realized using conventional technologies. However, the safety of such products is debated because of the potential risk of nanomaterials and lack of standardized guidelines for safely evaluating NF products. The global safety evaluations of nanomaterials focused on evaluating the cytotoxicity of zero-dimensional materials including nanoparticles and nanotubes based on OECD criteria. The NFs are one-dimensional materials with nanometer diameters and considerable lengths. Many fibers are applied in a densely woven web-like form, and therefore, assessing cellular penetration and fiber toxicity using the same methods is inappropriate. This study verifies the safety of polyurethane (PU) and polyvinylidene fluoride (PVDF) polymers, which are currently applied in filters and masks. To this end, polymer NFs were collected from each product, and the NFs were compared with reference samples considering their physical properties using FT-IR and Raman spectroscopy. For the safety evaluation, DMSO stocks of varying concentrations of PVDF and PU NFs (at 0.5, 1, 5, and 10 μg/mL) were prepared, and the cytotoxicity and inhibitory effects on nitric oxide production and protein expression obtained via Western blot were identified.

High circulating concentrations of the gut microbiota-derived metabolite trimethylamine N-oxide (TMAO) are significantly associated with the risk of obesity and type 2 diabetes (T2D). We aimed at evaluating the impact of glycemic control and bariatric surgery on circulating concentrations of TMAO and its microbiota-dependent intermediate, γ-butyrobetaine (γBB), in newly diagnosed T2D patients and morbidly obese subjects. An additional experiment was carried out in eight male C57BL/6J mice fed a Western-type diet for twelve weeks. The strategy for glycemic control in the T2D patients significantly improved the HbA1c concentrations without producing changes in the estimated glomerular filtration rate. However, the plasma TMAO and γBB concentrations were significantly increased following the glycemic control in T2D patients. Bariatric surgery was very effective in reducing weight in obese subjects. Nevertheless, the surgery reduced plasma γBB concentrations without affecting TMAO concentrations and the estimated glomerular filtration rate. Neither diet-induced obesity nor insulin resistance were associated with circulating TMAO and γBB concentrations in mice. Our findings do not support that glycemic control or bariatric surgery improve the circulating concentrations of TMAO in newly diagnosed T2D and morbidly obese patients. The contribution of antidiabetic drugs to gut microbiota composition could explain TMAO elevations in treated T2D subjects.

To verify the authors’ mathematical model for water jet cooling of steel sheet, the previously performed experimental studies of temperature of the test plate in the roller quenching machine (RQM) were used. The calculated data of steel temperature evolution along the RQM length were compared with the readings of thermocouples inserted in the center of the test plate and at its surfaces. The core of the model is the dependence of the temperatures of film, transition and nucleate boiling regimes on the thickness of the oxide scale layer on the cooled surface. It was found that the model correctly takes into account the oxide scale on the sheet surface, flow rates and combinations of the RQM banks used, water temperature and other factors. For all experiments the calculated metal temperature corresponds well to the measured one. In the experiments with interrupted cooling, the calculated temperature plots repeat the characteristic changes in the experimental curves. The main uncertainty in the modeling of cooling in a wide temperature range can be contributed by the random nature of changes in the oxide scale thickness during water cooling. In this regard, the estimated thickness of the oxide scale layer should be considered as the main parameter for adapting the sheet temperature control process. The obtained data confirm the possibility of effective application of the model in the ACS of industrial TMCP (Thermo-Mechanical Controlled Process) systems.

Non-viral gene carriers because of their limited side effects, biocompatibility, simplicity and taking the advantages of electrostatic interactions have shown noticeable potential in gene delivery. The low transfection rate of non-viral vectors under physiological conditions is a significant issue. Here, the aim of this study was to investigate the efficacy of hydrophilic and hydrophobic groups on gene carriers such as two synthesized amphiphilic polymer of dextran-stearic acid-spermine (DSASP) with verified lipid and amine conjugations that associated with Fe3O4 superparamagnetic nanoparticles to promote the target delivery and decrease the transfection time using static magnetic field. Our findings illustrate that magnetic nanoparticles are spherical with positive surface charges and superparamagnetic behaviors. The DSASP–pDNA/MNPs offered a strong pDNA condensation, protection against DNase degradation, significant cell viability in HEK 293T cells and. Although conjugations of spermine play a critical role in transfection efficiency, amphiphilic polymer with more derivatives of stearic acid showed better transfection yields. Therefore, DSASP amphiphilic magnetic carriers offer new insights for gene delivery due to the amine contents and ameliorate the uptake of complexes via cell membrane based on its hydrophilic surface.

With the advent of real-time MRI, the motion and passage of cerebrospinal fluid can be visualized without gating and exclusion of low-frequency waves. This imaging modality gives insights into low-volume, rapidly oscillating cardiac-driven movement as well as sustained, high-volume, slowly oscillating inspiration-driven movement.Inspiration means a spontaneous or artificial increase in the intrathoracic dimensions independent of body position. Alterations in thoracic diameter enable the thoracic and spinal epidural venous compartments to be emptied and filled, producing an upward surge of cerebrospinal fluid inside the spine during inspiration; this surge counterbalances the downward pooling of venous blood toward the heart.Real-time MRI, as a macroscale in vivo observation method, could expand our knowledge of neurofluid dynamics, including how astrocytic fluid preloading is adjusted and how brain buoyancy and turgor are maintained in different postures and zero gravity.Along with these macroscale findings, new microscale insights into aquaporin-mediated fluid transfer, its sensing by cilia and its tuning by nitric oxide will be reviewed. By incorporating clinical knowledge spanning several disciplines, certain disorders—congenital hydrocephalus with Chiari malformation, idiopathic intracranial hypertension and adult idiopathic hydrocephalus—are interpreted and reviewed according to current concepts, from the basics of the interrelated systems to their pathology.

Li-rich layered oxide cathode materials have become one of the most promising cathode materials for high-energy-density lithium-ion batteries owning to its high theoretical specific capacity, low cost, high operating voltage and environmental friendliness. Yet they suffer from severe capacity and voltage attenuation during prolong cycling, which blocks their commercial application. To clarify these causes, we synthesize 0.5Li2MnO3·0.5LiNi0.8Co0.1Mn0.1O2 (LL-811) with high-nickel-content cathode material by a solid-sate complexation method, and it manifests a lot slower capacity and voltage attenuation during prolong cycling compared to LL-111 and LL-523 cathode materials. The capacity retention at 1C after 100 cycles reaches to 87.5% and the voltage attenuation after 100 cycles is only 0.460 V. Combining X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM), it indicates that increasing the nickel content not only stabilizes the structure but also alleviates the attenuation of capacity and voltage. Therefore, it provides a new idea for designing of Li-rich layered oxide cathode materials that suppress voltage and capacity attenuation.

Titanium dioxide (TiO2) and aluminum oxide (Al2O3) coatings have been investigated in a wide range of bio-applications due to their biodegradation and biocompatibility properties, that are key parameters for their use in the food packaging and biomedical devices fields. The present study evaluates and compares the electrochemical behavior of the non-coated, commercial resin-coated, TiO2-coated and Al2O3-coated aluminum in commercial beer electrolyte. For this, TiO2 and Al2O3 thin films were deposited on aluminum (Al) substrates using atomic layer deposition (ALD). The evaluation of the corrosion barrier layer properties was performed by linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). In addition, profilometry, grazing incidence X-ray diffractometry (GIXRD), scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FT-IR) analyses were performed to investigate the physical and chemical properties of the pristine and / or corroded samples. TiO2 and Al2O3 films presented an amorphous structure, a morphology that follows Al substrate surface, and a thickness of around 100 nm. Analysis of LSV data showed that ALD coatings promoted a considerable increase in corrosion barrier efficiency being 86.3% for TiO2-coated Al and 80% for Al2O3-coated Al in comparison with 7.1% of commercial resin-coated Al. This is mainly due to the lower electrochemical porosity, 11.4% for TiO2-coated Al and 20.4% for Al2O3-coated Al in comparison with 96% of the resin-coated Al, i.e. an increase of up to twofold in the protection of Al when coated with TiO2 compared to Al2O3 coated. The EIS results allow us to complement the discussions about the reduced corrosion barrier efficiency of the Al2O3 film for beer electrolyte once SEM and FT-IR analyzes did not show drastic changes in both investigated ALD films after the corrosion assays. The above results indicate that ALD TiO2 and Al2O3 films may be a viable alternative to replace the synthetic resin coatings frequently used in aluminum cans of use in the food industry.

Water borne pathogens present a threat to human health and their disinfection from water poses a challenge, prompting search for newer methods and newer materials. Disinfection of Gram-negative bacterium Escherichia coli and Gram-positive coccal bacterium Staphylococcus aureus in aqueous matrix was achieved within 60 and 90 minutes respectively at 35⁰C using solar-photocatalysis mediated by sonochemically synthesized Ag@ZnO core-shell nanoparticles. The efficiency of the process increased with increase in temperature and at 55⁰C the disinfection could be achieved in 45 and 60 min respectively for the two bacteria. A new ultrasound assisted chemical precipitation technique was used for the synthesis of Ag@ZnO core-shell nanoparticles. The characteristics of the synthesized material were established using physical techniques. The material remained stable even at 400o C. Disinfection efficiency of the Ag@ZnO core-shell nanoparticles was confirmed in case of real world water samples from pond, river, municipal tap and was found to be better than that of pure ZnO and TiO2 (Degussa P25). When the nanoparticle based catalyst was recycled and reused for subsequent disinfection experiments, its efficiency did not change remarkably even after three cycles. The sonochemically synthesized Ag@ZnO core-shell nanoparticles have a good potential for application in solar photocatalytic disinfection of water borne pathogens.

Many stable water dispersions of various chemical compositions containing bioactive chemical compounds: copper silicate, titanium dioxide and zinc oxide (and other auxiliary substances) were developed and fabricated - they were used for preparation of thin hybrid coatings having very good antimicrobial properties against gram negative bacteria (Escherichia coli), gram positive bacteria (Staphylococcus aureus) and yeast fungus (Candida albicans). Polyester (PES) nonwovens were modified by dip-coating, and PES and cotton fabrics - by dip-coating and coating methods.

Titanium-based metal-matrix composites manufactured by additive manufacturing offer tremendous lightweighting opportunities. However, processing high reinforcement content remains challenging. This study reports an improved manufacturing process for Ti-TiC enabling high reinforcement content and significant fracture strain concurrently: mechanical blending, followed by laser powder bed fusion and a single heat treatment. As-built microstructure shows both un-melted TiC particles and sub-stoichiometric TiC dendrites resulting from a partial dissolution of TiC particles. The heat treatment is shown to fully convert TiC dendrites into equiaxed TiC grains. Reduction of the C/Ti ratio in TiC during the process results in an increase in the reinforcement content, from a nominal 12 vol% to an effective 21.5 vol%. Ti-TiC tensile samples reached fracture strains of up to 1.7%, Young’s moduli of up to 149 GPa and ultimate tensile strengths of up to 827 MPa. Lower TiC initial powder size distributions displayed the best mechanical performance.

This study outlines a 3-step production process for Ti-TiC Metal Matrix Composite (MMC) employing powder Mechanical Blending, Laser Powder Bed Fusion (LPBF), and a heat treatment. A TiC fraction of more than 20 vol% was formed in-situ through the reaction of titanium with carbon during the LPBF process. The manufactured MMC pieces showed a record stiffness and fracture strain combination. The LPBF energy density impacted strongly porosity type. The as-built microstructure displayed an homogeneous distribution of sub-stoichiometric TiC dendrites which were fully converted into equiaxed TiC grains during the heat treatment. The TiC C/Ti ratio was found to be close to 0.5, resulting in an effective reinforcement content nearly twice the one expected for stoichiometric TiC, leading to stronger reinforcement. The mechanical analysis revealed a Young’s modulus of up to 149 GPa and an ultimate tensile strength of up to 770 MPa, indicating a 27% and 34% improvement, respectively, compared to commercially pure Titanium produced by LPBF and heat treated in the same conditions. A fracture strain of up to 2.8% was achieved. The combination of in-situ formation of defect-free TiC reinforcement and subsequent heat treatment enables to reach an exceptional ductility, considering the 20 vol% reinforcement content.

Monte Carlo simulations were conducted to investigate the interaction between nucleation and the rates of chemical reduction in Au/Ag, Au/Pt and Au/Pd nanoparticles prepared in microemulsions using a one-pot method. The impact of nucleation on final nanostructure depends on the critical nucleus size value: at a high critical nucleus size, nucleation becomes the main factor in determining the final nanostructure, even with very large difference in reduction rates, as seen in the Au/Pd pair. However, when the critical nucleus size is small, the difference in reduction rates of the two metals becomes the key parameter determining the final nanostructure. Furthermore, the relevance of heteroatomic nucleation on the mechanism of nanoparticle formation depends on the difference between the reduction rates of the two metals. Smaller differences, such as in the Au/Ag or Au/Pt pairs, result in a greater impact of heteroatomic nucleation on the final nanostructure. In contrast, in the Au/Pd pair, heteroatomic nucleation becomes less important due to the low availability of Pd until late stages of synthesis. This study provides deeper insight into the complex mechanisms that govern reactions in microemulsions.

In metal additive manufacturing (AM), precise temperature field prediction is crucial for process monitoring, automation, control, and optimization. Traditional methods, primarily offline and data-driven, struggle with adapting to real-time changes and new process scenarios, which limits their applicability for effective AM process control. To address these challenges, this paper introduces the first physics-informed (PI) online learning framework specifically designed for temperature prediction in metal AM. Utilizing a physics-informed neural network (PINN), this framework integrates a neural network architecture with physics-informed inputs and loss functions. Pretrained on a known process to establish a baseline, the PINN transitions to an online learning phase, dynamically updating its weights in response to new, unseen data. This adaptation allows the model to continuously refine its predictions in real-time. By integrating physics-informed components, the PINN leverages prior knowledge about the manufacturing processes, enabling rapid adjustments to process parameters, geometries, deposition patterns, and materials. Empirical results confirm the robust performance of this PI online learning framework in accurately predicting temperature fields for unseen processes across various conditions. It notably surpasses traditional data-driven models, especially in critical areas like the Heat Affected Zone (HAZ) and melt pool. The PINN’s use of physical laws and prior knowledge not only provides a significant advantage over conventional models but also ensures more accurate predictions under diverse conditions. Furthermore, our analysis of key hyper-parameters—learning rate and batch size of the online learning phase—highlights their roles in optimizing the learning process and enhancing the framework’s overall effectiveness. This approach demonstrates significant potential to improve the online control and optimization of metal AM processes.

The fuel cell particularly the Proton Exchange Membrane Fuel Cell (PEMFC) is a new energy technology that plays a critical role in achieving market viability. The PEMFC has high power density, zero CO₂ emissions, and high conversion efficiency. However, with uniform distribution of fuel in PEMFC, we can improve the performance and reduce the cost. The PEMFC will be more efficient and effective in terms of renewable energy as a byproduct only water. Metal foam is used as an alternative for the channels in PEMFC. The model of PEMFC was established by using the ANSYS Fluent 3D Model. Then we proposed four configurations of PEMFC. The outcome demonstrates that Case IV provided outstanding performance if it is compared with the other three cases. In terms of power density, Case IV provided a high power density that is double that of Case I. The porosity of metal foam was investigated. The 0.6 porosity value is found as the optimal value. The uniform distribution of the fuel can be achieved at this value which leads to the outstanding current density.

This study investigates the potential benefits of integrating coarser particle size distributions (PSDs) of 45-106 µm into laser-based powder bed fusion of metals (PBF-LB/M), aiming to reduce costs while maintaining quality standards. Despite the considerable advantages of PBF-LB/M in producing intricate geometries with high precision, the high cost of metal powders remains a barrier to widespread adoption. By exploring the use of coarser PSDs, particularly from electron beam-based powder bed fusion of metals (PBF-EB/M), significant cost-saving opportunities are identified. Through comprehensive powder characterization, process analysis, and mechanical property evaluation, this study demonstrates that PBF-LB/M can effectively utilize coarser powders while achieving comparable mechanical properties to those produced with 20-53 µm PSD. Adaptations in process parameters enable the successful processing of coarser powders, maintaining high-relative density components with minimal porosity. Additionally, market surveys reveal substantial cost differentials between PBF-LB/M and PBF-EB/M powders, indicating 40 % cost reduction potential by integrating coarser PSDs into PBF-LB/M. Overall, this study provides valuable insights into the economic and technical feasibility of printing with coarser powders in PBF-LB/M, offering promising avenues for cost reduction without compromising quality, thus enhancing competitiveness and adoption of the technology in manufacturing applications.

Cancer cells show altered antioxidant defense systems, dysregulated redox signaling, and increased generation of reactive oxygen species (ROS). Targeting cancer cells through ROS-mediated mechanisms has emerged as a significant therapeutic strategy due to its implications in cancer progression, survival, and resistance. Extensive research has focused on selective generation of H2O2 in cancer cells for selective cancer cell killing by employing various strategies such as metal-based prodrugs, photodynamic therapy, enzyme-based systems, nano-particle mediated approaches, chemical modulators, and combination therapies. Many of these H2O2-amplifying approaches have demonstrated promising anticancer effects and selectivity in preclinical investigations. They selectively induce cytotoxicity in cancer cells while sparing normal cells, sensitize resistant cells, and modulate the tumor microenvironment. However, challenges remain in achieving selectivity, addressing tumor heterogeneity, ensuring efficient delivery, and managing safety and toxicity. To address those issues, H2O2-generating agents have been combined with other treatments leading to optimized combination therapies. This review focuses on various chemical agents/approaches that kill cancer cells via H2O2-mediated mechanisms. Different categories of compounds that selectively generate H2O2 in cancer cells are summarized, their underlying mechanisms and function are elucidated, preclinical and clinical studies as well as recent advancements are discussed, and their prospects as targeted therapeutic agents and their therapeutic utility in combination with other treatments are explored. By understanding the potential of these compounds, researchers can pave the way for the development of effective and personalized cancer treatments.

The recent green manufacturing demands have boosted the development of new biodegradable lubricants to replace petroleum-based lubricants. In this regard, water-based lubricants have been at the forefront of recent research for a wide range of industrial applications, including metalworking fluids (MWFs). In this work, we present an experimental investigation on the performance of novel green MWFs based on aqueous nopal mucilage solutions. For this, fully biodegradable solutions with different mucilage concentrations were evaluated in terms of rheological, tribological, thermal stability and turning (minimum quantity lubrication) performance, and compared to a commercial semisynthetic oil-based MWF (Cimstar 60). Mucilage solutions exhibited viscoelastic shear-thinning behavior, which was enhanced along with mucilage concentration. The solution with the highest mucilage content studied resulted in the lowest wear, friction and temperature in comparison to the other solutions and neat water in extreme pressure four-ball tests, and a similar level of lubricity as compared to the commercial MWF in cutting tests. This performance is associated to the enhanced viscosity and elasticity of the solution, as well as to the contents of lipids with fatty acids in the mucilage. Overall, the present results reveal the relevance of the viscoelastic behavior of the lubricant, elasticity in particular, in lubrication processes, and points to nopal mucilage as an effective green additive to produce innocuous MWFs.

Metal-organic frameworks (MOFs) represent the largest class of materials among the crystalline porous materials ever developed and have attracted attention as core materials for separation technology. Their extremely uniform pore aperture and nearly unlimited structural and chemical characteristics have attracted great interest and promise in applying MOFs to adsorptive and membrane–based separations. This paper reviews the recent research and development of MOF membranes for gas separation. Strategies for polycrystalline membranes and mixed matrix membranes are discussed, with a focus on separation systems involving hydrocarbon separation and CO2 capture. Challenges and opportunities for the industrial deployment of MOF membranes are also be discussed, providing guidance for the design and fabrication of future high-performance membranes. The contributions of the underlying mechanism to separation performances, and the adopted strategies and membrane processing technologies for breaking the selectivity/permeability trade–off are discussed.

Diamond-like carbon (DLC) films have a promising tribological application in green precision manufacturing, but their toughness represents a serious issue in the way of their application perspective. The film thickness is on the micrometer scale and makes conventional methods unsuitable for its toughness characterization. The absence of an accepted method for characterizing the DLC toughness has hindered the related research on the development of toughening methods and understanding the mechanism. This work intends to explore a relatively simple and acceptable characterization method to measure the film toughness. Moreover, toughening mechanisms of DLC films are proposed during the characterization to reveal the toughening mechanism. The toughness can be fully characterized through combining impact toughness and scratch toughness. The impact toughness can be obtained by observing the size of the indentation and the crack state around the indentation in the impact experiment. The scratch toughness could be assessed by combining the scratch morphology and Crack Propagation Resistance (CPRS). The improvement of film toughness should be carried out from two aspects: preventing microcrack initiation and suppressing crack propagation. Appropriate doping of non-carbide metal particles can effectively improve the toughness of the film, and there are seven main factors affecting the toughening of the film. Five toughening mechanisms of non-carbide metals from film preparation to test stage are revealed during the investigation of the change patterns.

This paper presents a comprehensive evaluation of metal foam employment within polymer electrolyte fuel cells (PEFCs) and compares it with conventional serpentine channels from both experiment viewpoints and computational fluid dynamics simulation. The experiments are designed to study the effects of material, area density, compression ratio, and final thickness of metal foam. Additionally, the influence of housing plate material and relative humidity (RH) is also tested for the first time. The results reveal that at RH=75-100%, the best distributor design is nickel foam with a compression ratio of 70%, a final thickness of 0.5mm, and SS-304 housing plate, which delivers 3110 mA cm^-2 as limiting current density that is scarce in the literature. The PEFC with this foam distributor shows a 10% improvement in maximum power density and 45% in limiting current density compared to the serpentine channel case. While at RH=30%, the same foam flow field with a final thickness of 1mm is a superior option. The experiments also indicate that maximum power density increases by 23% as the compression ratio rises from 0 to 70%, while reducing final thickness from 1 to 0.5 mm causes a 19% enhancement in cell performance. Simulation results reveal that metal foam is more successful in evenly reactant distribution so that the average oxygen mass fraction at the cathode catalyst layer is increased by 38% in the metal foam case compared to the serpentine channel.

: This article reports on polymer (PLLA, poly(L-lactic acid)) nanosheets incorporated with Fe-ion nanoparticles, aiming at using the latter nanoparticles as source to release Fe ions to facilitate burn wound healing when such nanosheets are applied on skin as biomedical tissue. Laser ablation in liquid phase was used to produce Fe-containing nanoparticles that after incorporation into PLLA nanosheets would release Fe ions when in immersed in water. Such nanoparticles prepared in chloroform are shown by XPS to be based on iron chloride and oxide phases. After incorporation into PLLA nanosheets, the ion –release test demonstrated that Fe ions could be released successfully into water at pH 7.4, which implies that such polymer nanosheets show promise for biomedical applications as potential patches for healing burn wounds. Incorporation with two different metal ions (Fe and Zn) is shown to be efficient and both types of ions were demonstrated to be released simultaneously and with comparable release rates.

Transition metal alloys have emerged as promising electrocatalysts due to their ability to modulate key parameters such as d-band electron filling, Fermi level energy, and interatomic spacing, thereby influencing their affinity towards reaction intermediates. However, the structural stability of alloy electrocatalysts during alkaline hydrogen evolution reaction (HER) remains a subject of debate. In this study, we systematically investigate the structural evolution and catalytic activity of the c-Co/Co3Mo electrocatalyst under alkaline HER conditions. We reveal that the instability of the Co3Mo alloy and H0.9MoO3 during alkaline HER leads to the destruction of the crystal structure, resulting in the formation of hexagonal cobalt (h-Co) from hexagonal Co(OH)2 as an intermediate species. Furthermore, we explore the re-adsorption and surface coordination of the Mo element, which enhances the catalytic activity for alkaline HER. This work provides valuable insights into the dynamic behavior of alloy-based electrocatalysts, shedding light on their structural stability and catalytic activity during electrochemical reduction processes

Fungal infection of grape berries (Vitis vinifera) by Botrytis cinerea frequently coincides with harvest, impacting both the yield and quality of grape and wine products. A rapid and non-destructive method for identifying B. cinerea infection in grapes at an early stage prior to harvest is critical to manage loss. In this study, zeolitic imidazolate framework-8 (ZIF-8) crystal was applied as an absorbent material for volatile extraction from B. cinerea-infected and healthy grapes in a vineyard followed by thermal desorption gas chromatography-mass spectrometry. The performance of ZIF-8 to absorb and trap targeted volatiles was evaluated with a standard solution of compounds and with a whole bunch of grapes enclosed in a glass container to maintain standard sampling conditions. Results from sampling methods were then correlated to B. cinerea infection in grapes as measured and determined by Genus specific antigen quantification. Trace levels of targeted compounds reported as markers of grape B. cinerea infection were successfully detected with in-field sampling. Peak area counts for volatiles 3-octanone, 1-octen-3-one, 3-octanol, and 1-octen-3-ol extracted using ZIF-8 were significantly higher than values achieved using Tenax®-TA from field testing and demonstrated good correlation with B. cinerea infection severities determined by B. cinerea antigen detection.

Novel TFN membranes were examined for the removal of heavy metals (Cu and Pb) from synthetic wastewater in forward osmosis (FO) experiments using MgCl2 as a draw solute. The TFN membranes were fabricated on top of a commercial PS35 ultrafiltration membrane by in-situ interfacial polymerization of piperazine (PIP) and 1,3,5-benzenetricarbonyl trichloride (TMC) containing different amounts of dispersed functionalized halloysite nanotubes (HNTs) nanoparticles. The HNTs nanoparticles were functionalized with the first generation of poly(amidoamine) (PAMAM) dendrimers. The TFN and the control TFC membranes showed rejections of Cu2+ and Pb2+, ranging from 94.5% to 98.1%. The presence of heavy metal in the feed solution enhanced the FO performance of all membranes. In particular, the reverse flux of MgCl2 decreased at least 2.5 times compared to the experiments with pure water as a feed. Simultaneously, the water flux also increased. The improved FO performance of the membranes in the presence of heavy metal ions is attributed to their adsorption by the membranes. The adsorption of heavy metals was confirmed by a decrease in the negativity of zeta potential and the results from inductively coupled plasma mass spectrometry (ICP-MS) of the membranes after the FO experiments.

During submerged laser peening using a pulsed laser, a bubble that behaves like cavitation is generated after laser ablation (LA). The bubble is referred to as laser cavitation (LC). The amplitude of the shock-wave in LA water is larger than that of LC; however, the impact passing through the target metal during LC is larger than that of LA. Thus, submerged laser peening is referred to as “laser cavitation peening”, as the peening method using the cavitation impact is known as “cavitation peening”. The impact induced by a hemispherical bubble is more aggressive than that of a spherical bubble with a microjet. Laser cavitation peening can improve the fatigue strength of metallic materials by producing work-hardening and the introduction of compressive residual stress. Three-dimensional additive manufactured metals (3D metals) such as titanium alloy are attractive materials for aviation components and medical implants; however, the fatigue strength of as-built components is nearly half that of bulk metals, and this is an obstacle for the applications of 3D metals. In the present study, published research papers were reviewed to identify the key factors of laser cavitation peening, with additional visualization of LC and data. Then, improvements in the fatigue strength of metallic materials, including 3D metals produced by laser cavitation peening, were summarized.

Metal-organic frameworks (MOFs), composed of metal nodes and inorganic linkers are promising for a wide range of applications due to their unique periodic frameworks that can be flexibly tuned. Understanding of the structure-activity relationships can facilitate the development and application of MOFs nanomaterials. Transmission electron microscopy (TEM) is a one-of-a-kind technique capable of characterizing MOFs microstructures at the atomic scale. Besides, in-situ TEM set-ups make it possible to direct visualize the microstructural evolution of MOFs in real time, which enables monitoring transitions of MOFs during growth as well as under working conditions. However, MOFs are so sensitive to the high-energy electron beam which makes TEM-based characterizing methods challenging. In this review, we first introduce the main damage mechanisms for MOFs under electron beam irradiation and two strategies to minimize the damages: low-dose TEM and cryo-TEM. Then, we discuss the techniques combined with the two strategies to analyze the MOFs’ microstructure, including three-dimensional electron diffraction, direct detection electron counting camera, and iDPC-STEM. Groundbreaking milestones and research advances with respect to static characterization of MOFs structures are highlighted. In-situ TEM studies are exemplary reviewed to provide insights into MOFs dynamics induced by various stimuli. Additionally, perspectives on promising techniques that may further facilitate the MOFs study using TEM are analyzed.

This research is aimed to develop the method for damage degree evaluation in metals and alloys during their deformation and destruction based on acoustic emission (AE) technique. Experimental studies were carried out on tensile specimens of high-strength steel with simultaneous registration of AE signals in tested material. It was shown that the time-dependent AE primary parameters, such as the AE signal maximum amplitudes and AE activity, do not have a clear relationship with the material damage degree. This fact makes it difficult to use standard methods for assessing the damage degree of acoustic signal sources, including defects. It was proposed to use the Kolmogorov-Smirnov criterion to differ the processes of metal plastic deformation and crack propagation during the rupture. The possibility of estimating the material damage degree by high-energy AE hits share was shown. Besides, a particular expression was obtained for evaluating the damage degree for the material under study.

Metallo-β-lactamases (MBLs) are a group of Zn(II)-dependent enzymes that pose a major threat to global health. They are linked to an increasing number of multi-drug resistant bacterial pathogens, but no clinically useful inhibitor is yet available. Since β-lactam antibiotics, which are inactivated by MBLs, constitute ~65% of all antibiotics used to treat infections, the search for clinically relevant MBL inhibitors is urgent. Here, derivatives of a 2-amino-1-benzyl-4,5-diphenyl-1H-pyrrole-3-carbonitrile (1a) were synthesised and their inhibitory effects assessed against representatives of each of the three subgroups of MBLs (B1, B2, B3). Several compounds are potent inhibitors of each MBL tested, making them excellent candidates for the development of broad-spectrum drug leads. In particular, compound 5f is highly potent across the MBL subfamilies, with Ki values in the low µM range. Furthermore, this compound also dis-plays synergy in combination with antibiotics such as penicillin G, cefuroxime or meropenem. This molecule thus represents one of the most promising compounds developed yet to combat MBLs.

Surfaces of additively manufactured metal parts from powder-based processes typically show powder particle agglomerations and other features, resulting in high surface roughness. Proper characterization of those surfaces is necessary in order to assess part quality with respect to coatability, mechanical performance or corrosion resistance for use in aerospace, automotive, medical and more industrial applications. Optical surface texture measurement allows for collection of areal surface data, while the established contact stylus method only captures line profile data. When applying optical methods for surface topography measurements, proper data acquisition and post-processing in order to assess surface texture may be complex. A number of variables can be adjusted, such as different measurement settings, approaches to outlier removal, evaluated area size or form removal. This work shows the influence of selected z-range prior to measurement and the influence of choosing pre-defined outlier removal settings in MountainsMap 9.2 on selected ISO 25178-2:2022 parameters calculated from data obtained from confocal microscopy for as-built Ti6Al4V from laser powder bed fusion. The aim is to show the influence of variation in measurement and post-processing on calculated surface texture parameters and stress the importance of proper documentation in order to achieve reproducibility of data for quality management.

Laser Powder Directed Energy Deposition (LP-DED) is an Additive Manufacturing process in which a laser beam is used to generate a melt pool onto a substrate. The additional material, in form of powder material, is fed into the generated melt pool and a raised track is obtained. The LP-DED process is very powerful for different applications such as the repair operations and the production of functionally graded material, however the application is still limited and one of the main reasons is related to the lack of knowledge in the physics of the process mechanisms. The process is influenced by a huge number of parameters and three main mechanisms can be identi-fied. These mechanisms are the powder flow, the generation of the molten pool and the solidifica-tion process and for each of these mechanisms the process parameters have a different relevance. In this paper, a review of the main mechanisms and the relationship between the process parame-ters and the outcome of each step of the process is presented.

This article presents, for the first time, the efficacy and curing depth analysis of photo-thermal dual polymerization in metal (Fe) polymer composites for 3D printing of a 3-component (A/B/M) system based on the proposed mechanism of our group, in which the co initiators A and B are Irgacure-369, and charge-transfer complexes (CTC), respectively; and the monomer M is filled by Fe. Our formulas show the depth of curing (Zc) is an increasing function of the light intensity, but a decreasing function of the Fe and photoinitiator concentrations. Zc is enhanced by the additive [B] which produces extra thermal radical for polymerization under high temperature. The heat (or temperature) increase in the system has two components : (i) due to the light absorption of Fe filler, and (ii) heat released from the exothermic photopolymerization of the monomer. The heat is transported to the additive (or co-initiator) [B] to produce extra radical R' and enhance the monomer conversion function (CF). The Fe filler leads to temperature increase, but also limits the light penetration leading to lower CF and Zc, which could be overcome by the additive initiator [B] in thick polymers. Optimal Fe for maximal CF and Zc are explored theoretically.

Three-Dimensional mesoporous TiO2 scaffolds of anatase phase possess inherent eximious optical behavior that are beneficial in designing photoelectrodes for solar energy conversion applications. However, substantial efforts have been devoted in maximizing the UV and/or visible light absorption efficiency, and suppressing the annihilation of photogenerated charged species in pristine mesoporous TiO2 structure for improved solar illumination conversion efficiencies. This study provides the fundamental insights into Mxene functionalized mesoporous TiO2 as photoelectrode for the first time. This novel combination of Mxene functionalized TiO2 electrodes with and without TiCl4 treatments have been successfully optimized to intensify the process of photon absorption, charge segregation and photocurrent, resulting in superior photoelectrode performance. The photocurrent measurements of prepared photoelectrodes are significantly enhanced upon increased contents of Mxene due to improved absorption efficiency within the visible region as verified by UV–Vis absorption spectroscopy. Moreover, as evident through structural analysis, the anatase phase of TiO2 is well grown due to increased contents of Mxene and post-deposition heat treatments. Consequently, an appreciable coverage of well-developed grains on FTO surface observed in SEM images. Thereby, the newly fabricated conductive mesoporous TiO2 photoelectrodes are potential candidates for photoinduced energy conversion and storage purposes.

A critical challenge underpinning the adoption of Additive Manufacture (AM) as a technology is the postprocessing of manufactured components. For Selective Laser Sintering (SLS) this can involve the removal of powder from the interior of the component, often by vibrating the component to fluidise the powder to encourage drainage. In this paper we develop and validate a computational model of the flow of metal powder suitable for predicting powder removal from such AM components. The model is a continuum Eulerian multiphase model of the powder including models for the granular temperature; the effect of vibration can be included through appropriate wall boundaries for this granular temperature. We validate the individual sub-models appropriate for AM metal powders by comparison with in-house and literature experimental results, and then apply the full model to a more complex geometry typical of an AM Heat Exchanger. The model is shown to provide valuable and accurate results at a fraction of the computational cost of a particle-based model.

A new strategy to nanoengineer gold/fluorocarbon multilayer (ML) nanostructures is reported. We have investigated the morphological changes occuring at the metal-polymer interface in multilayer structures with varying volume fraction of gold (Au) and the kinetic growth aspect of the microscale properties of nano-sized Au in plasma polymer fluorocarbon (PPFC). Investigations were carried out at various temperatures and annealing time by means of grazing incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS). We have fabricated a series of multilayers with variying volume fraction (0.12, 0.27, 0.38) of Au and bilayer periodicity in ML structure. They show an interesting granular structure consisting of nearly spherical shaped nanoparticles within the polymer layer. The nanoparticle (NP) morphology changes due to the collective effects of NPs diffusion within ensembles in the in-plane vicinity and inter-layer with increasing temperature. The in-plane NPs size distinctly increases (from 1.9 to 4 nm) with increasing temperature. The NPs become more spherical thus reducing the surface energy. Linear growth of NPs with temperature and time shows diffusion-controled growth of NPs in the ML structure. The structural stability of the multilayer is controlled by the volume ratio of the metal in polymer. At room temperature UV-Vis shows a blueshift of the plasmon peak from 560 nm in ML Au/PTFE_1 to 437 nm in Au/PTFE_3. We have identified the fabrication and post-deposition annealing conditions to limit the Local Surface Plasmon resonance (LSPR) shift (from 〖∆λ〗_LSPR=180 nm (Au/PTFE_1) to 〖∆λ〗_LSPR=67 nm (Au/PTFE_3 ML)) and their optical response over a wide visible wavelength range. A variation in the dielectric constant of the polymer in precence of varying Au inclusion is found to be the main factor affecting the LSPR frequency. Our finding may provide insights in Nano engineering ML structure can be useful to systematically control the growth of NPs in polymer matrix.

The use of the LMD technology as a manufacturing and repairing technique in industrial sectors like the die and mold and aerospace is increasing within the last decades. Research carried out in the field of LMD process situates argon as the most usual inert gas, followed by nitrogen. Some leading companies have started to use helium and argon as carrier and shielding gas, respectively. There is therefore a pressing need to know how the use of different gases may affect the LMD process due to there is a lack of knowledge with regard to gas mixtures. The aim of the present work is to evaluate the influence of a mixture of argon and helium on the LMD process by analyzing single tracks of deposited material. For this purpose, special attention is paid to the melt pool temperature, as well as to the characterization of the deposited clads. The increment of helium concentration in the gases of the LMD processes based on argon will have three effects. The first one is a slightly reduction of the height of the clads. Second, an increase of the temperature of the melt pool. Last, smaller wet angles are obtained for higher helium concentrations.

Metal hydrides are one of the types of functional materials that allow safe and compact storage of a large amount of hydrogen, which is increasingly used today as an alternate fuel or energy source. The possibility of obtaining the initial energy necessary for the production of hydrogen by electrolysis process from renewable energy sources, such as solar panels and wind generators, makes hydrogen energetic quite attractive and rapidly developing industry sector. Solid form of hydrogen storage with the possibility of reversible sorption, gives opportunity for creation autonomous energy storage systems. La-Ni based alloys allow hydrogen storing at ambient temperatures and pressure not higher than 15 bar, which makes the application of these alloys quite practical, interesting and prospects for analysis and modifications on the ways of stored hydrogen capacity increasing, alloys price reducing and application for renewable energy storage.

The article considers the issues of ensuring operational performance and environmental sustainability of marine diesel engines by using biodiesel fuel. The research was conducted on 5S60ME-C8 MAN-B&W Diesel Group and 6DL-16 Daihatsu Diesel marine diesel engines, which were operated using RMG380 petroleum fuel and B10 and B30 biodiesel fuels. The efficiency of biofuel usage was assessed based on environmental (reduced nitrogen oxide concentration in exhaust gases) and economic (increased specific effective fuel consumption) criteria. It was found out that the use of B10 and B30 biofuels provides reduction of nitrogen oxides concentration in exhaust gases by 14.71–25.13 %, but at the same time increases specific effective fuel consumption by 1.55–6.01 %. Optimum fuel injection advance angles were determined that ensure the best thermal energy, economic and environmental performance of diesel engines. The optimum angle of biofuel supply advance is determined experimentally and should correspond to the limits recommended by the diesel engine operating instructions. It has been proven experimentally that the use of biofuel increases the environmental sustainability of marine diesel engines by 13.75–29.42 %. It increases the diesel engines environmental safety in case of emergency situations, as well as accidental and short-term emissions of exhaust gases with an increased content of nitrogen oxides into the atmosphere - phenomena that are possible in starting modes of diesel engine operation, as well as in modes of sudden load changes. It is the increase in the environmental friendliness of marine diesel engines in the case of using biofuel that is the most positive criterion and contributes to the intensity of biofuel use in power plants of sea vessels.

Finishing coatings in the wood-based composites industry not only influence the final appearance of the product but also serve to protect against fungi, and molds, and reduce the release of harmful substances, particularly formaldehyde and volatile organic compounds (VOCs). Carbon-rich materials, such as those derived from birch bark extraction, specifically suberin acids, can fulfil this role. Previous research has demonstrated that adding suberin acid residues (SAR) at 20% and 50% by weight significantly enhances the gas barrier properties of surface finishing materials based on poly(lactide) (PLA) and polycaprolactone (PCL), particularly in terms of Total VOC (TVOC) and formaldehyde emissions. This study aims to explore whether these properties can be further improved through the incorporation of nano-zinc oxide (nano-ZnO). Previous research has shown that these nanoparticles possess strong resistance to biological factors and can positively affect the characteristics of nanofilms applied as surface protection. The study employed PLA and PCL finishing layers blended with SAR powder at 10% w/w and included 2% and 4% nano-zinc oxide nanoparticles. The resulting blends were milled to create a powder, which was subsequently pressed into 1 mm thick films. These films were then applied to raw particleboard surfaces. TVOC and formaldehyde emission tests were conducted. Additionally, the fungal resistance of the coated surfaces was assessed. The results showed that PLA/SAR and PCL/SAR composites with the addition of nano-zinc oxide nanoparticles exhibited significantly improved barrier properties, offering a promising avenue for developing biodegradable, formaldehyde-free coatings in the furniture industry with enhanced features. Furthermore, by utilizing SAR as a post-extraction residue, this project aligns perfectly with the concept of upcycling.

The pharmaceutical industry usually utilizes either hydrophobic or hydrophilic substances extracted from raw plant materials for preparing a final product, However, the plant material waste still contain substances with an opposite solubility. The aim of this study was to enhance the comprehensive usability of plant materials by developing a new non-wasting extraction method for eucalypt leaves and by investigating the phytochemical and pharmacological properties of eucalypt extracts and their 3D-printed dosage forms. The present extraction method enabled to prepare both hydrophobic soft extracts and hydrophilic (aqueous) dry extracts. We identified total 28 terpenes in the hydrophobic soft extract. In the hydrophilic dry extract, total 57 substances were identified, and 26 of them were successfully isolated. The eucalypt extracts studied showed a significant antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa, Bacillus subtilis, Candida albicans, Corynebacterium diphtheriae gravis, and Corynebacterium diphtheriae mitis. The anti-inflammatory activity of the dry extract was studied with a formalin oedema model in mice. The maximum anti-exudative effect of the dry extract was 61.5% at a dose of 20 mg/kg. The composite gels of polyethylene oxide and eucalypt extract were developed, and the key process parameters for semi-solid extrusion (SSE) 3D printing of such gels were verified. The SSE 3D-printed preparations of novel synergistically acting eucalypt extracts could have uses in antimicrobial and anti-inflammatory medicinal applications.

Pretreatment of cells with proteolysis inhibitors diminished intensity and changed shape of DNICs specific EPR signal in a treatment time-dependent manner. The level of DNIC formation was significantly influenced by the presence of protein degradation products. Interestingly, formation of HMWDNICs depended on the availability of LMWDNICs. The extent of glutathione involvement in the in vivo formation of DNICs is minor yet noticeable, aligning with our prior research findings.

In this work, nanocomposite photoelectrodes of the TiO2/ Au composition were manufactured, in which the size of plasmonic Au nanoparticles was varied, and the morphology of the TiO2 layer, depending on the thickness, changed from an island to a continuous layer. The influence of the morphology of plasmonic Au nanoparticles and the TiO2 layer on the optical and photoelectrochemical characteristics of hybrid photoelectrodes was studied. It has been shown that continuous coating of Au nanoparticles with a TiO2 layer (layer thickness 10 and 15 nm) leads to a decrease in the photoelectric response, and the decrease in photocurrent density and photoconversion efficiency decreases in proportion to the thickness of the TiO2 layer. The indicated drop in characteristics when plasmonic particles are located under the TiO2 layer is presumably associated with the scattering and recombination of charge carriers in the semiconductor layer. The best performance was shown by a system in which large Au nanoparticles (10 nm) are coated with a 5 nm thick layer of titanium dioxide; in this geometry, Au nanoparticles are decorated with TiO2 nanoparticles, as a result of which the photoelectrode-electrolyte interface has a more complex structure.

Biomass exploitation is a global trend due to the circular economy and the environmentally friendly spirit. Numerous applications are now based on the use of biomass derived products. Hydrogen sulfide (H2S) is a highly toxic and environmentally hazardous gas, which emitted from various processes. Thus, the efficient removal of this toxic hazardous gas following cost effective processes is an essential requirement. In this study, we present the synthesis and characterization of biomass-derived activated-carbon/zinc-oxide (ZnO@AC) composites from different biomass sources as potential candidates for H2S sorption. The synthesis involved a facile method for activated carbon production via pyrolysis and chemical activation of biomass precursors (spent coffee, Aloe-Vera waste leaves, and corncob). Activated carbon production was followed by the incorporation of zinc oxide nanoparticles into the porous carbon matrix using a simple melt impregnation method. The synthesized ZnO@AC composites were characterized using X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and nitrogen porosimetry. The H2S removal performance of the ZnO@AC composites was evaluated through sorption experiments using a handmade apparatus. Our findings demonstrate that the Aloe-Vera, Spent-coffee, and Corncob derived composites exhibit superior H2S sorption capacity up to 106 mgH2S/gads., 66 mgH2S/gads., and 47 mgH2S/gads. respectively.

It has been well known for a long time that inert gases, such as xenon (Xe), have significant biological effects. As these atoms are extremely unlikely to partake in direct chemical reactions with bio-molecules, such as proteins, lipids and nucleic acids, there must be some other mode of action to account for the effects reported. It has been shown that the topology of proteins allows for cavities and hydrophobic pockets, and it is through an interaction with such protein structures that inert gases are thought to have their action. Recently, it has been mooted that the relatively inert gas molecular hydrogen (H2), also may have its effects through such a mechanism, and so influencing protein structures and actions. H2 is thought to also act through interaction with redox active compounds, particularly the hydroxyl radical (·OH) and peroxynitrite (ONOO-), but not nitric oxide (NO·), superoxide anions (O2·-) or hydrogen peroxide (H2O2). However, instead of having a direct interaction with H2, is there any evidence that these redox compounds can also interact with Xe pockets and cavities in proteins, so either having an independent effect on proteins or interfering with the action of inert gases. This suggestion with be explored here.

In this study the formation of thin-film barrier coatings based on a highly-conducting Bi1.60Er0.4O3 (EDB) solid electrolyte on supporting Ce0.8Sm0.2O1.9 (SDC) electrolyte substrates is implemented for the first time using electrophoretic deposition (EPD). Electrokinetic properties of EDB-based suspensions in a non-aqueous dispersion medium of isopropanol modified with small additions of polyethyleneimine (PEI, 0.26 g/L) and acetylacetone (0.15 g/L), as well as in a mixed isopropanol/acetylacetone (70/30 vol.%) medium are studied. The dependences of the thickness of EDB coatings on voltage and deposition time are obtained using deposition on a model Ni-foil electrode. Preliminary synthesis of a conductive polypyrrole (PPy) polymer film is used to create surface conductivity of non-conductive SDC substrates. The efficiency of using a modified dispersion medium based on isopropanol to obtain a continuous EDB coating 12 μm thick, sintered at a temperature of 850 °C for 5 h, is shown. The microstructure and morphology of the surface of the EDB coating are studied. Pt/SDC/EDB/Pt cell is used to characterize the coating conductivity. The EPD method is shown to be promising for the formation of barrier coatings based on doped bismuth oxide. The developed method can be used for creating cathode barrier layers in SOFC technology.

The present study was aimed at revealing the influence of the mechanical stress induced by water molecules adsorption on the composition of crystalline phases in the ZrO2–3mol%Y2O3-nanoparticles. Three basic methods have been used to determine the phase transition: neutron diffraction, Raman microspectroscopic scanning, and X-ray diffraction. The fact of phase-structural β → α transformation and the simultaneous presence of two polymorphic structural modifications (β is the phase of the tetragonal syngony and α of monoclinic syngony in nanosized particles (9nm)) under normal physical conditions was established by these methods. Satisfactory consistency was achieved between the results obtained using different techniques.

Poly(2-methoxyethyl acrylate) (PMEA) and poly(ethylene oxide) (PEO) have protein-antifouling properties and blood compatibility. ABA triblock copolymers (PMEAn-PEO11340-PMEAn (MEOMn)) were prepared using single-electron transfer-living radical polymerization (SET-LRP) using a bi-functional PEO macroinitiator. Two types of MEOMn composed of PMEA blocks with a degree of polymerization (DP = n) of 85 and 777 were prepared using the same PEO macroinitiator. MEOMn formed flower micelles with a hydrophobic PMEA (A) core and hydrophilic PEO (B) loop shells in diluted water with a similar appearance to petals. The hydrodynamic radii of MEOM85 and MEOM777 were 151 and 108 nm, respectively. The PMEA block with a large DP formed a tightly packed core. The aggregation number (Nagg) of the PMEA block in a single flower micelle for MEOM85 and MEOM777 was 156 and 164, respectively, which were estimated using a light scat-tering technique. The critical micelle concentrations (CMCs) for MEOM85 and MEOM777 were 0.01 and 0.002 g/L, respectively, as determined by the light scattering intensity and fluorescence probe techniques. The size, Nagg, and CMC for MEOM85 and MEOM777 were almost the same inde-pendent of hydrophobic DP of the PMEA block.

rdinary people and political leaders must know the sources of greenhouse gas emissions and their effect on global climate change before they have ability to make decisions to reduce emissions and increase sinks of these gases. These people must, however, understand where greenhouse gas emissions are formed and how reductions can be made: they must understand where carbon dioxide sinks are and how to preserve or increase these sinks. North Savo is the example used in this work to describe the present emissions and sinks. There are proposals on what should and could be done to reduce greenhouse gas emissions caused by traffic, heating, forests and agriculture. There are possibilities of reducing emissions of greenhouse gases in traffic and heating in spite of the fact that the province has a low population density with long distances between homes and workplaces and schools, and a cold climate. We believe that research will also find solutions for reducing greenhouse gases and protecting waters, which are used for recreational purposes and for raw water of drinking water in many places. Luckily forests cover large areas of North Savo and their growth is an important carbon dioxide sink. In addition, forest soils serve as a valuable storage of carbon. Besides carbon dioxide emissions, emissions of nitrous oxide and methane must also be considered since they are more potent greenhouse gases than carbon dioxide and land use can thus influence these gas emissions.

Replacing carbon by hydrogen is a huge step towards reducing CO₂ emissions in the iron- and steel-making industry. The reduction of iron oxides using hydrogen plasma smelting reduction as an alternative to conventional steel-making routes has been studied at Montanuniversitaet Leoben, Austria. The aim of this work was to study the slag formation during the reduction process and the reduction behaviour of iron oxides. Furthermore, the reduction behaviour of iron ore during continuous feeding was assessed. Mixtures of iron ore and calcined lime with a basicity of 0, 0.8, 1.6, 2.3, and 2.9 were melted and reduced by hydrogen. The off-gas composition was measured during the operations to calculate the process parameters. The reduction parameters, namely the degree of reduction, degree of hydrogen utilisation, produced iron, and slag, are presented. The results of the batch-charged experiments showed that at the beginning of the reduction process, the degree of hydrogen utilisation was high, and then, it decreased over the operation time. In contrast, during the continuous-feeding experiment, the degree of hydrogen utilisation could be kept approximately constant. The highest degrees of reduction and hydrogen utilisation were obtained upon the application of a slag with a basicity of 2.3. The experiment showed that upon the continuous feeding of iron ore, the best conditions for the reduction process using hydrogen could be applied.

Lithium-rich layered oxides is one of the most perspective candidates for cathode materials of lithium ion battery, because of its high discharge capacity. However, there are some disadvantages of uneven composition, voltage decay, and poor rate capacity, which are closely related to the preparation method. Here, 0.5Li2MnO3·0.5LiMn0.8Ni0.1Co0.1O2 were successfully prepared by sol-gel and oxalate co-precipitation methods. A systematic analysis of the materials shows that the 0.5Li2MnO3·0.5LiMn0.8Ni0.1Co0.1O2 prepared by the oxalic acid co-precipitation method has the most stable layered structure and the best electrochemical performance. The initial discharge specific capacity is 261.6 mAh·g-1 at 0.05 C, and the discharge specific capacity is 138 mAh·g-1 at 5 C. The voltage decay is only 210 mV, and the capacity retention is 94.2% after 100 cycles at 1 C. The suppression of voltage decay can be attributed to the high nickel content and uniform element distribution. In addition, tightly packed porous spheres help to reduce lithium ion diffusion energy and improve the stability of the layered structure, thereby improving cycle stability and rate capacity. This conclusion provides a reference for designing high energy density lithium-ion batteries.

Tungsten oxides play a pivotal role in a variety of modern technologies e.g., switchable glasses, wastewater treatment, and modern gas sensors. Metallic tungsten is used as armor material, for e.g., gas turbines as well as future fusion power devices. In the first case, oxides are desired as functional materials, while in the second case, oxides can lead to catastrophic failures, so avoiding the oxidation of tungsten is desired. In both cases, it is crucial to understand the reactivity of tungsten oxides with other chemicals. In this study, the different reactivities of tungsten oxides with the highly-oxophilic beryllium are studied and compared. Tungsten-(IV)-oxide and tungsten-(VI)-oxide layers are prepared on a tungsten substrate. In the next step, a thin film of beryllium is evaporated on the samples. In consecutive steps, the sample is heated in steps of 100 K from r. t. to 1273 K. The chemical composition is investigated after each experimental step by high-resolution X-ray photoelectron spectroscopy (XPS) of all involved core levels as well as the valence band. A model is developed to analyze the chemical reactions after each step. In this study, we find that tungsten trioxide was already reduced by beryllium at r. t. and started to react to form the ternary compounds BeWO₃ and BeWO₄ at temperatures starting from 673 K. However, tungsten dioxide is resistant to reduction at temperatures of up to 1173 K. In conclusion, we find WO₂ to be much more chemically resistant to the reduction agent Be than WO₃.

Citrus peel has been used in Asian traditional medicine for the treatment of cough, asthma, and bronchial disorders. However, the anti-inflammatory effect of quercetogetin (QUE), a polymethoxylated flavone isolated from the peel of citrus unshui is poorly understood. We investigated the anti-inflammatory effect and the molecular mechanisms of QUE in lipopolysaccharide (LPS)-induced RAW264.7 cells. QUE inhibited the production of NO and prostaglandin E2 by suppressing the LPS-induced expression of inducible nitric oxide synthase and cyclooxygenase-2 at both the mRNA and protein levels. QUE suppressed the production of proinflammatory cytokines, such as interleukin (IL)-1β, IL-6, and tumor necrosis factor-α. QUE also inhibited the translocation of the nuclear factor kappa B subunit, p65, into the nucleus by interrupting the phosphorylation of IκB-α in LPS-induced RAW 264.7 cells. Based on the finding that QUE significantly decreased p-ERK protein expression in LPS-induced RAW264.7 cells, we confirmed that suppression of the inflammatory process by QUE was mediated through the MAPK pathway. This is the first report on the strong anti-inflammatory effects of QUE, which is a compound that can potentially be used as a therapeutic agent for inflammatory diseases.

Immunosensors have been widely developed to use antibodies to detect a pathogen of interest; it is interesting to look at the effect of nonspecific antibody binding to E. coli using electrochemical methods. IgG antibody not specific to E. coli O157:H7 was crosslinked onto a screen-printed carbon electrode. The presence of E. coli at 4, 4 × 10², 4 × 10⁵, and 4 × 10⁸ CFU/mL on the electrode surface was detected via linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Current transfer at both electrodes was reduced as the concentration of bacteria increased; however, the calibration of number of cells to decreased current was nonlinear for IgG-modified electrodes. The nonlinearity is confirmed by EIS measurements which showed highest impedance at 4 CFU/mL E. coli when impedance should be the lowest. FESEM images showed higher binding of cells when IgG is present compared to electrodes with reduced graphene oxide (rGO) alone. Electrodes with rGO alone show less attachment of E. coli, with EIS showing a linear calibration profile, while LSV shows not much difference in current values for all concentrations aside from the highest concentration. These results suggest that nonspecific binding can provide false signals in electrochemical measurements, and it is crucial to provide proper controls.

One of the relevant goals in forging technologies is simplifying the existing process and developing new processes that can retain the original or very close to the original dimensions and billet shape after the end of the deformation cycle. This study attempts to develop a forging equipment design that provides alternating cyclic loading; the alternate cyclic forging (ACF) method is proposed. To preliminary evaluate the ACF and study the plastic deformation behavior, numerical simulation via finite element modeling (FEM) was conducted using DEFORM-3D. The main attention was paid to the metal flow characteristics, effective strain and stress distribution, and the forging load. The ACF results in non-uniform metal flow with the formation of diagonal and vortex flows were demonstrated. Maximum effective strains and stresses zones are localized at two points of the billet contact with the surface of the tooling container and at two points of the interface between the punches. It was also assumed that reducing the contact area between the punch and the billet using separate semi-cylindrical punches can reduce the forging load. Preliminary finite element analysis (FEA) results of the proposed process after four successive steps of the deformation cycle confirmed the feasibility of its general implementation.

Lithium-metal batteries offer high energy density, but are challenged by dendrite growth, which can lead to short circuits and battery failure. Various models with varying degrees of accuracy and computational cost have been developed to understand and predict dendrite growth. In this study, a simple simulation model to predict macroscale dendrite growth on lithium metal electrodes is presented. The model uses a 3D single-particle diffusion-limited aggregation (DLA) algorithm, biased by the electric field, to simulate dendrite growth. The model was validated using 3D MRI of dendrite growth in a lithium symmetric cell. It was used to simulate deposition between consecutive measured dendrite structures. The model also introduces an important parameter, namely the biasing factor c, which determines the balance between diffusion and electric field effects. This parameter was calibrated using the overlap and displacement of deposition sites metrics, achieving optimal results at c = 0.7. The model predictions were in good agreement with experimental data confirmed by fractal dimension analysis. This model provides a useful tool for predicting and studying dendrite formation in lithium and other metal batteries.

Objective: This study aimed to assess the impact of artificial intelligence (AI)-driven noise reduction algorithms on metal artifacts and image quality parameters in cone-beam computed tomography (CBCT) images of the oral cavity. Materials and Methods: This retrospective study included 70 patients, 61 of whom were analyzed after excluding those with severe motion artifacts. CBCT scans, performed using a Hyperion X9 PRO 13 × 10 CBCT machine, included images with dental implants, amalgam fillings, orthodontic appliances, root canal fillings, and crowns. Images were processed with ClariCT. AI deep learning model (DLM) for noise reduction. Objective image quality was assessed using metrics such as the differentiation between voxel values (ΔVVs), the artifact index (AIx), and the contrast-to-noise ratio (CNR). Subjective assessments were performed by two experienced readers, who rated overall image quality and artifact intensity on predefined scales. Results: Compared with native images, DLM reconstructions significantly reduced the AIx and increased the CNR (p<0.001), indicating improved image clarity and artifact reduction. Subjective assessments also favored DLM images, with higher ratings for overall image quality and lower artifact intensity (p<0.001). However, the ΔVV values were similar between the native and DLM images, indicating that while the DLM reduced noise, it maintained the overall density distribution. Orthodontic appliances produced the most pronounced artifacts, while implants generated the least. Conclusion: AI-based noise reduction using ClariCT. AI significantly enhances CBCT image quality by reducing noise and metal artifacts, thereby improving diagnostic accuracy and treatment planning. Further research with larger, multicenter cohorts is recommended to validate these findings.

With the ever-growing emphasis on global decarbonization and rapid increases in the power density of electronics equipment in recent years, new methods and lightweight materials have been developed to manage heat load as well as interfacial stresses associated with Coefficient of Thermal Expansion (CTE) mismatch between components. The Al-Si system provides an attractive combination of CTE performance and high thermal conductivity whilst being a very lightweight option. Such materials are of interest to industries where thermal management is a key design criterion, such as aerospace, automotive, consumer electronics, defense, EV and space. This paper will describe the development and manufacture of a family of high-performance hypereutectic Al-Si alloys (AyontEX™) by a powder metallurgy method. These alloys are of particular interest for structural heat sink applications that require high reliability under thermal cycling (CTE of 17μm/(m·°C)) as well as reflective optics and instrument assemblies that require good thermal and mechanical stability (CTE of 13μm/(m·°C)). Critical performance relationships are presented, coupled with the microstructure, physical and mechanical properties of these Al-Si alloys.

Transition metal complexes have historically played a pivotal role in creating vibrant pigments utilized across artistic mediums such as ceramics, paintings, and glass mosaics. Despite their extensive historical use, our understanding of the mechanisms governing transition metal complex behavior has predominantly emerged in recent times, leaving numerous aspects of this process ripe for exploration. These complexes exhibit striking color variations under diverse conditions when employed in pigment formulations. This review utilizes a bottom-up scientific approach, spanning from microscopic to macroscopic scales, to unravel the molecular origins of the colors generated by transition metal complexes in pigments and ceramic glazes. Advanced spectroscopy techniques and computational chemistry play pivotal roles in this endeavor, highlighting the significance of understanding and utilizing analytical data effectively, with careful consideration of each technique's specific application. Furthermore, the review investigates the influence of processing conditions on color variations, providing valuable insights for artists and manufacturers aiming to enhance the precision and quality of their creations while mitigating environmental impact.

Dissimilar welds between ferritic and austenitic steels represent a good solution for exploiting the best performance of stainless steels at high and low temperatures and in aggressive environments, while minimizing costs. Therefore, they are widely used in nuclear and petrochemical plants, however, due to the different properties of the steels involved, the welding process can be challenging. Fusion welding can be specifically addressed to connect low-carbon, or low-alloy steels, with high-alloy steels, which have similar melting point. Welding of thick plates can be performed with electric arc in multiple passes or in a single pass by means of a laser beam equipment. Since microstructure and consequently mechanical properties of the weld are closely related to composition, the choice of the filler metal and processing parameters, which in turn affects the dilution rate, plays a fundamental role. Numerous technical solutions were proposed for welding dissimilar steels and much research was developed on the weldment metallurgy; therefore, this article is aimed at a review of the most recent scientific literature on the issues relating to the fusion welding of ferritic / austenitic steels. Two specific sections are dedicated respectively to electric arc and laser beam welding; finally, metallurgical issues, related to dilution and thermal field are debated in the discussion section.

Contrast agents developed for X-ray computed tomography (CT) offer extremely valuable tools and techniques in diagnostics via contrast enhancements. Heavy metal-based nanoparticles (NPs) can provide high contrast in CT images. These result from a high density of heavy metal atoms with high X-ray attenuation coefficients that exceed that of iodine (I), which is currently used in hydrophilic organic CT contrast agents. Nontoxicity and colloidal stability are vital characteristics in designing heavy metal-based NPs as CT contrast agents. In addition, the particle size must be small for in vivo renal excretion. In vitro phantom imaging studies can provide X-ray attenuation efficiency, which is a critical parameter for CT contrast agents, and the imaging performance of CT contrast agents can be demonstrated via in vivo experiments. This review focuses on in vitro and in vivo studies of various heavy metal-based NPs (metal: Au, Pt, Pd, Ag, Ce, Gd, Dy, Ho, Yb, Ta, W, and Bi) and provides an outlook on their use as high-performance CT contrast agents.

The response of plasmonic metal particles to an electromagnetic wave undergoes significant features at the nanoscale level. Different properties of the internal composition of a metal, such as its ionic background and the free electron gas, begin to manifest more prominently. As the dimensions of the nanostructures decrease, the classical local theory gradually becomes inadequate. Therefore, Maxwellʹs equations need to be supplemented with a relationship determining the dynamics of current density which is the essence of nonlocal plasmonic models. In this field of physics, the standard (linearized) hydrodynamic model (HDM) has been widely adopted with great success, serving as the basis for a variety of simulation methods. However, ongoing efforts are also being made to expand and refine it. Recently, the GNOR (general nonlocal optical response) modification of the HDM has been used, with the intention of incorporating the influence of electron gas diffusion. Clearly, from the classical description of fluid dynamics, a close relationship between viscosive damping and diffusion arises. This offers a relevant motivation for introducing the GNOR modification in an alternative manner. The standard HDM and its existing GNOR modification also do not include the influence of interband electron transitions in the conduction band and other phenomena that are part of many refining modifications of the Drude‐Lorentz and other models of metal permittivity. In this article, we present a modified version of GNOR‐HDM that incorporates the viscosive damping of the electron gas and a generalized Drude‐Lorentz term. In the selected simulations, we also introduce Landau damping which corrects the magnitude of the standard damping constant of the electron gas based on the size of the nanoparticle. We have chosen a spherical particle as a suitable object for testing and comparing HD models and their modifications because it allows finding precise analytical solutions for the interaction and, simultaneously, it is a relatively easily fabricable nanostructure in practice. Our contribution also includes our own analytical method for solving the HDM interaction of a plane wave with a spherical particle. This method forms the core of calculations of the characteristic quantities, such as the extinction cross‐sections and the corresponding components of electric fields and current densities.

This short review is aimed at giving an overview of catalytic carbonylative double cyclization reactions, which are processes in which suitable organic substrates and carbon monoxide are sequentially activated by a promoting catalyst to afford the formation of two new cycles with concomitant incorporation of carbon monoxide as a carbonyl function into the final product. Paradigmatic examples of this powerful synthetic methodology, which allows the one-step synthesis of complex molecular architectures from simple building blocks using the simplest and readily available C-1 unit (CO) are illustrated and discussed. The review is divided into five sections: 1) Introduction; 2) Functionalized Olefinic Substrates; 3) Functionalized Acetylenic Substrates; 4) Functionalized Halides; 5) Conclusions and Future Perspectives.

The paradigm of drug delivery via nano- and microcarriers is one of the leading ideas that enable overcoming the limitations of traditional chemotherapy. The trend toward more complex drug carriers capable of multifunctionality is observed in the literature. To date, prospects of stimuli-responsive systems to control the cargo release in the lesion nidus are widely accepted. Both endogenous and exogenous stimuli are employed for this purpose, however, endogenous pH is one of the most common triggers. Unfortunately, scientists face difficulties in the implementation of this idea since a range of biological barriers, drug bioavailability issues, and challenges in the synthesis of carriers with required properties have arisen. Here, we discuss fundamental strategies of pH-responsive drug delivery as well as limits in its application and reveal the main problems, weak sides, and reasons for poor clinical results. Also, we have made an attempt to formulate the profiles of "ideal" drug carrier in the frame of different strategies and considered recently published studies through the lens of these profiles. This approach enables the identification of current trends and promising vectors in the development of pH-responsive drug delivery systems, as well as challenges to be resolved in the next generation of carriers.

Plazomicin is a recently U.S. Food and Drug Administration (FDA)-approved semisynthetic aminoglycoside. Its structure consists of a sisomicin scaffold modified by adding a 2(S)-hydroxy aminobutyryl group at the N1 position and a hydroxyethyl substituent at the 6′ position. These substitutions produced a molecule refractory to most aminoglycoside-modifying enzymes. The main enzyme within this group that recognizes plazomicin as substrate is the aminoglycoside 2′-N-acetyltransferase type Ia [AAC(2′)-Ia], which reduces the antibiotic’s potency. Designing formulations that combine an antimicrobial with an inhibitor of resistance is a recognized strategy to extend the useful life of existing antibiotics. We have recently found that several metal ions inhibit acetylation of numerous aminoglycosides catalyzed by the aminoglycoside 6′-N-acetyltransferase type Ib [AAC(6′)-Ib]. In particular, Ag1+, which also enhances the effect of aminoglycosides by other mechanisms, is very effective in interfering with AAC(6′)-Ib-mediated resistance to amikacin. Here we report that silver acetate is a potent inhibitor of AAC(2′)-Ia-mediated acetylation of plazomicin in vitro, and it reduces resistance levels of Escherichia coli carrying aac(2′)-Ia. The resistance reversion assays produced equivalent results when the structural gene was expressed under the control of the natural or the blaTEM-1 promoters. The antibiotic effect of plazomicin in combination with silver was bactericidal, and the mix did not show significant toxicity to human embryonic kidney 293 (HEK293) cells.

Residual stresses in fiber metal laminates (FML) inevitably develop during the manufacturing process. The main contributor to these stresses is the difference in the coefficients of thermal expansion (CTE) between fibers and metal in combination with high process temperatures. To quantify these stresses, the use of specimens with an asymmetric layup is an easily adaptable method. The curvature that develops after the manufacturing of flat laminates with an asymmetrical layer stack is a measure of the level of residual stresses evolving during cure. However, the accuracy of the curvature evaluation is highly dependent on specimen design and other influencing parameters. In this work a large set of FML specimens is investigated to identify relevant influencing parameters and derive conclusions about specimen design and evaluation techniques. For certain layups and process parameters, there is a good correlation between the curvature and the stress-free temperature, which is further covered by analytical solutions for bimetals. This correlation is the basis to transfer curvature into a stress-free temperature that can consequently be used for the quantification of residual stress levels in more complex FMLs. The transfer is validated by in-situ strain measurements during cure using a strain gage technique. Based on the results, the application of asymmetric specimens for residual stress characterization in more complex laminates is presented in the form of a workflow.

Structural health monitoring of lightweight constructions made of composite materials can be performed using guided ultrasonic waves. If modern fiber metal laminates are used, this requires integrated sensors that can record the inner displacement oscillations caused by the propagating guided ultrasonic waves. Therefore, we have developed a robust MEMS vibrometer that can be integrated with structural and functional compliance. This vibrometer is directly sensitive to the high-frequency displacements from structure-borne ultrasound when excited between its first and second natural frequency. The vibrometer is mostly realized by processes earlier developed for a pressure sensor but with additional femtosecond laser ablation and wafer bonding. The piezoresistive transducer made from silicon is encapsulated between top and bottom glass lids. The natural frequencies are experimentally determined using an optical micro vibrometer setup. The vibrometer functionality and usability for structural health monitoring are demonstrated on a customized test rig by recording application-relevant guided ultrasonic wave packages with a central frequency of 100 kHz at a distance of 200 mm from the exciting ultrasound transducer.

Radially polymerized dendritic compounds are nowadays an established polymer category next to their linear, branched and cross-linked counterparts. Their uncommon tree-like architecture is characterized by adjustable internal cavities and external groups. They are therefore exceptional absorbents and this attainment of high concentrations into their interior renders them ideal reac-tion media. In this framework they are applied in many environmentally benign implementa-tions. One of the most important among them is water purification though pollutant decomposi-tion. Simple and composite catalysts and photo-catalysts containing dendritic polymers and ap-plied in water remediation will be discussed jointly with some unconventional solutions and fu-ture prospects.

For the better part of a century researchers across disciplines have sought to explain the crystallography of the elemental transition metals: hexagonal close packed, body centered cubic, and face centered cubic in a form similar to that used to rationalize the structure of organic molecules and inorganic complexes. Pauling himself tried with limited success to address the origins of transition metal stability. These early investigators were handicapped, however, by incomplete knowledge regarding the structure of metallic charge density. Here we exploit modern approaches to charge analysis to first comprehensively describe transition metal charge density. Then, we use topological partitioning and quantum mechanically rigorous treatments of kinetic energy to account for the structure of the density as arising from the interactions between metallic tetrahedra. We argue that the crystallography of the early transition metals results from charge transfer from the so called “octahedral” to “tetrahedral holes” while the face centered cubic structure of the late transition metals is a consequence of antibonding interactions that increase octahedral hole kinetic energy.

Non steady applied magnetic field impact on a liquid metals has good prospects for industry. For a better understanding of heat and mass transfer processes under these circumstances, numerical simulations are needed. A combination of finite elements and volumes methods was used to calculate the flow and solidification of liquid metal under electromagnetic influence. Validation of numerical results was carried out by means of measuring with ultrasound Doppler velocimetry technique, as well as with neutron radiography snapshots of the position and shape of the solid/liquid interface. As a result of the first part of the work, a numerical model of electromagnetic stirring and solidification was developed and validated. This model could be an effective tool for analyzing the electromagnetic stirring during the solidification process. In the second part, the dependences of the velocity pulsation amplitude and the melt velocity maximum value on the magnetic field pulsation frequency are obtained. It was found numerically the ability of the pulsating force action to develop higher values of the liquid metal velocity at a frequency close to the MHD resonance. Obtained characteristics give a more detailed description of the electrically conductive liquid behaviour under action of pulsating traveling magnetic field.

The recovery of precious metals is a project with both economic and environmental significance. In this paper, it presents how to use bacterial mineralization to selectively recover gold from multi-ionic aqueous systems. The Bacillus licheniformis FZUL-63, separated from a landscape lake in FuZhou University, was shown to selectively mineralize and precipitate gold from coexisting ions in aqueous solution. The removal of Au(III) was almost happened in first hour, and FTIR data show that the amino, carboxyl and phosphate groups on the surface of the bacteria are related to the adsorption of gold ions. XPS results implied that Au(III) ions are reduced to monovalent, and then the Au(I) was adsorbed on the bacterial surface at the beginning stage(first hour). XRD results showed the gold biomineralization began about 10 hours after the interaction between Au(III) ions and bacteria. The Au(III) mineralization has been rarely influenced by other co-existing metal ions. TEM analysis shows the gold nanoparticles are polyhedral structure with a particle size of ~20 nm. The Bacillus licheniformis FZUL-63 could selectively mineralize and recover 478 mg/g(dry biomass) gold from aqua regia-based metal wastewater through four cycles. It could be of great potential in the practical application.

We summarize structural instabilities exhibited by the one dimensional (1D) (arene)2X family of organic conductors in relation with their electronic and magnetic properties. With a charge transfer of one electron to each anion X these salts exhibit a quarter-filled (hole) conduction band located on the donor stacks. Compounds built with donors such as fluorenthene and perylene derivatives and anions X such PF6 or AsF6 exhibit a high temperature (TP~170K) conventional Peierls transition which is announced by a sizeable regime of 1D 2kF charge density wave fluctuations (kF is the Fermi wave vector of the 1D electron gas located on Per stacks). Surprisingly, and probably because of the presence of a multi-sheet warped Fermi surface, the Peierls transition is considerably reduced in the perylene series α-(Per)2[M(mnt)2] where X is the dithiolate molecule with M=Au, Cu, Co and Fe. A special attention is devoted in this paper to physical properties of α-(Per)2[M(mnt)2] salts which with M=Pt, Pd and Ni incorporate segregated S=1/2 1D antiferromagnetic (AF) dithiolate stacks with 1D metallic Per stacks. We analyse conjointly the structural and magnetic properties of these salts in relation with the 1D spin-Peierls (SP) instability located on the dithiolate stacks. We show that the SP instability of the Pd and Ni derivatives occurs in the classical (adiabatic limit) while the SP instability of the Pt derivative occurs in the quantum (anti-adiabatic limit). Furthermore we show that in the Pd and Ni derivatives frustrated 1st neighbour direct and 2nd neighbour indirect (through a fine tuning with the mediated 2kF RKKY coupling interaction on Per stacks) AF interactions add their contribution to the SP instability to open a singlet-triplet gap. Our analysis of the data show unambiguously that magnetic α-(Per)2[M(mnt)2] salts are a typical realization of the physics predicted for two chain 1D Kondo lattices.

The article presents the results of studies aimed to identify the effect of foliar treatments of winter wheat, sugar beets and soybeans with mineral and bioorganic fertilizers. Their positive effect on increasing the concentration of mineral forms of nitrogen in soil was revealed. The crop types have a greater influence on the size of nitrous oxide emissions: in winter wheat crops - 679 µg/m3, soybeans - 637.2 µg/m3, sugar beets - 576.8 µg/m3. The amounts of nitrous oxide emissions were lower in the variants without the use of phosphorus-potassium fertilizers. The Ruter AA fertilizer showed the greatest efficiency on winter wheat crops - 42.7 c/ha. Soybean grain yield of 44.2 c/ha was also achieved by using Ruter AA, as well as Geo-humate together with phosphorus-potassium fertilizers. On the background of the actual supply of phosphorus and potassium, maximum yield was obtained when using N30 on the leaf - 39.3 c/ha. Foliar feeding ensured a yield of sugar beet root crops of up to 67.1-77.4 c/ha on the backdrop of the application of phosphorus-potassium fertilizers with the advantage of using Amino turbo. The largest yield of sugar beet roots without use of mineral phosphorus and potassium was ensured by N30 treatment of the leaf in the phases of 4-6 and 8 leaves - 63.2 t/ha. Of the organo-mineral fertilizers and biostimulants, the best result was shown by the use of Ruter A - 62.6 t/ha. We believe that foliar feeding of crops can be a sustainable farming method that can increase crop yields and reduce N2O emissions.

Numerous structures at the nano- and microscale manifest distinctive properties with far-reaching implications across diverse fields, including electronics, electricity, medicine, and surface engi-neering. Established methods such as nanoimprint lithography, photolithography, and self-assembly play crucial roles in the fabrication of nano- and microstructures; however, they exhibit limitations in generating high-aspect-ratio structures when utilizing high-viscosity pho-tocurable resins. In response to this inherent challenge, we propose a highly cost-effective ap-proach facilitating the direct replication of high-aspect-ratio structures, specifically nanowires, through the utilization of anodized aluminum substrates. This study elucidates the streamlined fabrication process for multiscale porous surfaces achieved through the evaporation-induced in-tegration of solid nanowires printed with high-viscosity photocurable resin.

The reduction of Ce cations in CeO2 can be enhanced by its partial substitution by Fe cations. The enhanced reduction of Ce cations results in a considerable increase in the reaction rates for thermal water splitting reaction when compared to CeO2 alone. This mixed oxide has a smaller crystallite size when compared to CeO2 in addition to a smaller lattice size. In this work, two Fe-substituted Ce oxides are studied (Ce0.95Fe0.05O2 and Ce0.75Fe0.25O2) by core and valence level spectroscopy in their as-prepared and Ar-ions sputtered states. Ar-ions sputtering substantially increases Ce4f lines at about 1.5 eV below the Fermi level. In addition, it is found that the XPS Ce5p/O2s ratio is sensitive to the degree of reduction, most likely due to a higher charge transfer from the oxygen to Ce ions upon reduction. Quantitatively it is also found that XPS Ce3d of the fraction of Ce3+ (uo, u’ and vo, v’) formed upon Ar-ions sputtering and the ratio Ce5p/O2s lines are higher for reduced Ce0.95Fe0.05O2 than for reduced Ce0.75Fe0.25O2. XPS Fe2p showed however no preferential increase for Fe3+ reduction to Fe0 with increasing time for both oxides. Since water splitting was higher on Ce0.95Fe0.05O2 when compared to Ce0.75Fe0.25O2, it is inferred that the reaction centers for the thermal water splitting to hydrogen are the reduced Ce cations and not the reduced Fe cations. These reduced Ce cations can be tracked by their XPS Ce5p/O2s ratio in addition to the common XPS Ce3d lines.

Four leather substrates from different animals were treated by dispersions containing hydrophilic composite silica-hyperbranched poly(ethylene imine) xerogels. Antimicrobial activity was introduced by incorporating silver nanoparticles and /or benzalkonium chloride. The gel precursor solutions were also infused before gelation to titanium oxide powders typically employed for induction of self-cleaning properties. The dispersions from these biomimetically premade xerogels integrate environmentally friendly materials with short coating times. Scanning electron microscopy (SEM) provided information on the powder distribution onto the leathers. Substrate and coating composition were estimated by infrared spectroscopy (IR) and ener-gy-dispersive X-ray spectroscopy (EDS). Surface hydrophilicity and water permeability were assessed by water-contact angle experiments. The diffusion of the leather's initial components and xerogel additives into the water were measured by Ultraviolet-Visible (UV-Vis) spectroscopy. Protection against GRAM- bacteria was tested for Escherichia coli, Pseudomonas aeruginosa, and Klebsiella Pneumoniae against GRAM+ bacteria for Staphylococcus aureus, and Enterococcus faecalis and against fungi for Candida albicans. Antibiofilm capacity experiments were performed against Staphylococcus aureus, Klebsiella Pneumoniae, Enterococcus faecalis, and Candida albicans. The application of xerogel dispersions proved an adequate and economically feasible alternative to the direct gel formation into the substrate’s pores for the preparation of leathers intended for medical uses

It is now well accepted that most chronic diseases have a common feature which is “low-grade” inflammation. Whether inflammation is causal or rather consequent to these diseases is still a matter of debate. A key factor of inflammation is considered to be “oxidative stress”, which is the result of an alteration of redox homeostasis which is critical for the regulation of physiological cell and organ metabolism and proliferation. The term “oxidative stress” is how-ever often used in an inappropriate manner as the primary target of the initial oxidative radical, superoxide ion, is nitric oxide which, being in large excess, acts as a “buffer”, yielding reactive nitrogen species. It is only once the superoxide fluxes exceed the nitric oxide fluxes that true “oxidative stress” occurs. Nitro-oxidative stress is a more appropriate term which takes into account the evolving generation of reactive nitrogen and oxygen species and their effects on cell and organ pathophysiology. The molecular bases of redox homeostasis and nitro-oxidative stress will be presented and discussed using obesity-linked inflammation as a path-ophysiological example.

Nitric oxide (NO) is a key molecule in cardiovascular homeostasis and its abnormal delivery is highly associated with the occurrence and development of cardiovascular disease (CVD). The assessment and manipulation of NO delivery is crucial to the diagnosis and therapy of CVD, such as endothelial dysfunction, atherosclerotic progression, pulmonary hypertension, and cardiovascular manifestations of Coronavirus (COVID-19). However, due to the low concentration and fast reaction characteristics of NO in cardiovascular system, the clinical applications centered on the NO delivery are challenging. In this tutorial review, we first summarized the methods to estimate the in vivo NO delivery process based on the clinical images and mathematical modeling to assess the endothelial function and vulnerability of atherosclerotic plaque. Then, the emerging bioimaging technologies that have the potential to directly measure the arterial NO concentration were discussed, including the Raman spectroscopy and electrochemical sensor. Aside from the diagnostic methods, therapies aimed at controlling NO delivery to regulate CVD were reviewed, including the inhaled NO therapy to treat the pulmonary hypertension and COVID-19, stem cell therapy and NO-releasing platform to treat endothelial dysfunction and atherosclerosis.

Transparent conducting oxides (TCO) with high electrical conductivity and at the same time high transparency in the visible spectrum are an important class of materials widely used in many devices requiring a transparent contact such as light-emitting diodes, solar cells and display screens. Since the improvement of electrical conductivity usually leads to degradation of optical transparency, a fine-tuning sample preparation process and a better understanding of the correlation between structural and transport properties is necessary for optimizing the properties of TCO for use in such devices. Here we report a structural and magnetotransport study of tin oxide (SnO₂), a well-known and commonly used TCO, prepared by a simple and relatively cheap Atmospheric Pressure Chemical Vapour Deposition (APCVD) method in the form of thin films deposited on soda-lime glass substrates. The thin films were deposited at two different temperatures (which were previously found to be close to optimum for our setup), 590 °C and 610 °C, and with (doped) or without (undoped) the addition of fluorine dopants. Scanning Electron Microscopy (SEM) and Grazing Incidence X-ray Diffraction (GIXRD) revealed the presence of inhomogeneity in the samples, on a bigger scale in form of grains (80–200 nm), and on a smaller scale in form of crystallites (10–25 nm). Charge carrier density and mobility extracted from DC resistivity and Hall effect measurements were in the ranges 1–3 × 10²⁰ cm⁻³ and 10–20 cm²/Vs, which are typical values for SnO₂ films, and show a negligible temperature dependence from room temperature down to -269 °C. Such behaviour is ascribed to grain boundary scattering, with the interior of the grains degenerately doped (i.e., the Fermi level is situated well above the conduction band minimum) and with negligible electrostatic barriers at the grain boundaries (due to high dopant concentration). The observed difference for factor 2 in mobility among the thin-film SnO₂ samples most likely arises due to the difference in the preferred orientation of crystallites (texture coefficient).

Bone cement, mainly based in PMMA, is commonly used in different arthroplasty surgical proce-dures, and its use is essential for prosthesis fixation. However, its manufacturing process reaches high temperatures that can produce necrosis in the patients' surrounding tissues. In order to con-tribute to avoid this problem, the addition of graphene could delay the polymerisation of the MMA and, simultaneously, contribute to the optimisation of the composite material's properties. This article analysed the effect of the addition of different percentages of Highly Reduced Graphene Oxide (HRGO) with different wt. % (0,10, 0,50 and 1,00) and surface densities (150, 300, 500 and 750 m2/g) on the physical, mechanical, and thermal properties of commercial PMMA-based bone cement and its processing. It was noticed that a lower sintering temperature would be reached with this addition, making it less harmful to use in surgery and as it reduces its adverse effects. In contrast, the materials' density does not show significant changes, which indicates that the addi-tion of HRGO does not significantly increase its porosity. Lastly, the mechanical properties are re-duced by almost 20 %. Nevertheless, these properties are high enough so that these new materials can still fulfil their structural function.

The development of hydrogen plasma smelting reduction as a CO₂ emission-free steel-making process is a promising approach. This study presents a concept of the reduction of hematite using hydrogen thermal plasma. A laboratory scale and pilot scale hydrogen plasma smelting reduction (HPSR) process are introduced. To assess the reduction behavior of hematite, a series of experiments has been conducted and the main parameters of the reduction behavior, namely the degree of hydrogen utilization, degree of reduction and the reduction rate are discussed. The thermodynamic aspect of the hematite reduction is considered and the pertinent calculations have been carried out using FactSage^TM 7.2. The degree of hydrogen utilization and the degree of reduction were calculated using the off-gas chemical composition. The contribution of carbon, introduced from the graphite electrode, ignition pin and steel crucible, to the reduction reactions was studied. The degree of reduction of hematite, regarding H₂O, CO and CO₂ as the gaseous reduction products, is determined. It is shown that the degree of hydrogen utilization and the reduction rate were high at the beginning of the experiments, then decreased during the reduction process owing to the diminishing of iron oxide. Conducting experiments with the high basicity of slag B₂=2 led to a decrease of the phosphorus concentration in the produced iron.

In the present work, we report on a 3D MOF of {[Pb5(3-OH)(3-NO3)3(6-pmdc)3·H2O}n formula (pmdc = pyrimidine-4,6-dicarboxylate) synthesized by an oven-heated solvent-free procedure. The large connectivity afforded by the three ligands in their coordination to lead(II) ions grows cubic building units characterized by a central Pb atom with an unusual coordination index of 12 and six pmdc ligands occupying the faces. These cubic units are linked one another giving rise to a quite condensed structure that represents an unprecedented topology showing the (4.62)6(43)2(45.610)3(45.68.82)6(46.69)6(612.83) point symbol. The crystalline material has been characterized by routine physico-chemical techniques to confirm its purity and its thermal behaviour has been also studied by thermogravimetric and thermodiffractometric analyses. The solid presents greenish blue photoluminescent emission based on pmdc ligands, as revealed time-dependent density-functional theory (TD-DFT) calculations, by that is substantially more intense than in free H2pmdc ligand according to its improved quantum yield. The emissive capacity of the material is further analysed according to decreasing temperature of the polycrystalline sample, finding that sizeable long-lasting phosphorescence is present.

The paper presents the development of cheap and selective Paper-based Analytical Devices (PADs) for Pd(II) determination. The PADs were obtained with an azoic ligand, (2-(tetrazolylazo)-1,8 dihydroxy naphthalene-3,6,-disulphonic acid), termed TazoC, and filter paper as the substrate. The orange TazoC-PADs interact quickly with Pd(II) solutions by forming a complex purple-blue-colored already at a very acidic pH (lower than 2). The dye complexes no other metal ions at such an acidic media, making TazoC-PADs highly selective to Pd(II) detection. Besides, at higher pH values, other cations, for example, Cu(II) and Ni(II), can interact with TazoC through the formation of stable and pink-magenta-colored complexes; however, it is possible to quantify Pd(II) also in the presence of other cations using a multivariate approach. Indeed, by applying Partial Least Square regression (PLS), the spectra of the TazoC-PADs were related to the Pd(II) concentrations both when present alone in solution and also in the presence of Cu(II) and Ni(II). The PLS models correctly predicted Pd(II) concentrations in unknown samples and tap water spiked with the metal cation.

The flavin derivatives 10‐methyl‐isoalloxazine (MIA) and 6-fluoro-10-methyl-isoalloxazine (6F-MIA) were encapsulated in two alternative metal-organic frameworks, (MOFs) MIL53(Al) and MOF5, using a post-synthetic, diffusion-based incorporation into microcrystalline MIL-53 powders and an in-situ approach during the MOF-5 synthesis. The flavin@MOF composites were analyzed by powder X-ray diffractometry (PXRD), N2-sorption studies and time-resolved fluorescence spectroscopy and microscopy. The maximum amount of flavin dye incorporation is 3.9 wt% for MIA@MIL-53(Al) and 1.5 wt% for 6F-MIA@MIL-53(Al), 0.85 wt% for MIA@MOF-5 and 27.6 wt% for 6F-MIA@MOF-5. The emission wavelengths of all flavin@MOF composites mostly correspond to the wavelengths of the flavins in solution. Time-resolved spectroscopy showed that the fluorescence lifetime of flavin@MOF of 2-4.7 ns also corresponds to those in solution but is significantly prolonged compared to the solid flavin dyes with less than 1 ns, thereby confirming the concept of "solid solutions" for dye@MOF composites. The fluorescence quantum yield (ΦF) of the flavin@MOF composites is about half of the solution but is significantly higher compared to the solid flavin dyes. Both the fluorescence lifetime and quantum yield of flavin@MOF decrease with the flavin loading in MIL-53. Theoretical calculations using plane-wave and QM/MM methods are in good correspondence with the experimental results and explain the electronic structures as well as the photoluminescence/photophysical properties of crystalline MIA and the flavin@MOF composites. In the solids flavins π-stacking interactions of the molecules lead to a charge transfer state with low oscillator strength resulting in aggregation-caused quenching (ACQ) with low lifetimes and quantum yields. In the MOF pores the flavin molecules are separated and the computed MIA@MOF structures do not find π-stacking interactions to the pore walls but only weak van-der-Waals contacts which reasons the enhanced fluorescence lifetime and quantum yield of the flavins in the composites compared to their neat solid state. The flexible MOF MIL-53(Al) was optimized essentially to the experimental large-pore form in the guest-free state with QuantumEspresso (QE) and with MIA molecules in the pores the structure contracted to close to the experimental narrow-pore form which was also confirmed by PXRD. In summary, the incorporation of flavins in MOFs yields solid-state materials with enhanced rigidity, stabilized conformation and reduced aggregations of the flavins, leading to increased fluorescence lifetime and quantum yield as controllable photo-luminescent and photo-physical properties.

This paper focuses on parametric model order reduction (PMOR) of guided ultrasonic wave propagation and its interaction with damage in a fiber metal laminate (FML). Structural health monitoring in FML seeks to detect, localize and characterize the damage with high accuracy and minimal use of sensors. This can be achieved by the inverse problem analysis approach which employs the signal measurement data recorded by the embedded sensors in the structure. The inverse analysis requires to solve the forward simulation of the underlying system several thousand times. These simulations are often exorbitantly expensive and triggered the need for improving their computational efficiency. A PMOR approach hinged on the proper orthogonal decomposition method is presented in this paper. An adaptive parameter sampling technique is established with the aid of a surrogate model to efficiently update the reduced-order basis in a greedy fashion. A numerical experiment is conducted to illustrate the parametric training of the reduced-order model. The results show that the reduced-order solution based on the PMOR approach is accurately complying with that of the high fidelity solution.

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2’-bis(aminomethyl)-1,1’-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = 5-C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium with retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to 67% ee.

Penicillium digitatum is the major postharvest pathogen of citrus fruit under Mediterranean climate conditions. In the present work, we have addressed the study of the role of P. digitatum’s proteases in virulence following two complementary approaches. In a first approach, we have undertaken the functional characterization of the P. digitatum prtT gene, which codes for a transcription factor previously shown to regulate extracellular proteases in other filamentous fungi. Deletion of prtT caused a significant loss in secreted protease activity during in vitro growth assays. However, there was no effect on virulence. Gene expression of the two major secreted acid proteases was barely affected in the ΔprtT deletant during infection of citrus fruit. Hence, no conclusion could be drawn on the role of these secreted acidic proteases on the virulence of P. digitatum. In a second approach, we have studied the effect of different protease inhibitors and chelators in virulence. Co-inoculation of citrus fruit with P. digitatum conidia and a cocktail of protease inhibitors resulted in almost a complete absence of disease development. Analysis of individual inhibitors revealed that the metalloprotease inhibitor 1,10-phenanthroline was responsible for the observed effect. The application of metal ions reverted the protective effect caused by the metallopeptidase inhibitor. These results may set the basis for the development of new alternative treatments to combat this important postharvest pathogen.

There is much interest in effective copper chelators to correct copper dyshomeostasis in neurodegenerative and oncological diseases. In this study, a recombinant fusion protein for expression in E. coli cells was constructed from glutathione-S-transferase (GST) and the N-terminal domain (ectodomain) of human high affinity copper transporter CTR1 (hNdCTR1), which has three metal-bound motifs. Several biological properties of the GST-hNdCTR1 fusion protein were assessed. It was demonstrated that in cells, the protein was prone to oligomerization, formed inclusion bodies and displayed no toxicity. Treatment of E. coli cells with copper and silver ions reduced cell viability in a dose- and time-dependent manner. Cells expressing GST-hNdCTR1 protein demonstrated resistance to the metal treatments. These cells accumulated silver ions and formed nanoparticles that contained AgCl and Ag0. In this bacterial population, filamentous bacteria with length about 10 μm were often observed. The possibility for the fusion protein carrying extracellular metal binding motifs to integrate into the cell’s copper metabolism and its chelating properties are discussed.

This work focuses on the theoretical study of the effect of entanglement in the Yttrium Barium Copper Oxide (YBCO) superconductor on the critical current density, critical magnetic field, and penetration depth. Using the Ginzburg Landau (GL) theory, the expression for the GL coherence length, the critical current density, the lower critical magnetic field (Hc1), and the upper critical magnetic field (Hc2) for the entangled superconducting YBCO was obtained. At zero external magnetic fields, YBCO was found to undergo a transition from the normal state to the superconducting state at 93K and returned to normal. We found a direct relationship between the GL coherence length penetration depth and the temperature of the entangled superconducting YBCO. The graphs of the lower critical magnetic field (Hc1) and critical current density against temperature show a non-linear dependence.In contrast, the graph of the upper critical magnetic field (Hc2) against temperature (T) shows the linear dependence, which is in agreement with existing theoretical observations. On the other hand, the graph of critical current density against the distance of separation between the entangled electrons that form a cooper pair showed that the critical current density increases between 1.8 and 6 nanometers attaining a constant value after reaching 7 nanometers for infinite distances. Finally, for lower critical fields, the magnetic field decreases between 1.5 to 6 nanometers attaining a constant value of the magnetic field, for infinite values of distance of separation between the entangled pair of electrons.

Cryopreserved semen is widely used in Assisted Reproductive Technologies (ART) enabling the conservation and broad use of genetically superior semen. The quality of semen post-thawing determines the success of ART and despite the great advances in cryopreservation methods, the quality of frozen/thawed semen is still sub-optimal. Post-thawing spermatozoa endure oxidative stress (OS) due to the high levels of reactive oxygen and nitrogen species, which are produced during the freezing/thawing process, and the depletion of antioxidants. To counteract this depletion, supplementation of sperm preparation medium with antioxidants has been widely applied. Melatonin is a hormone with diverse biological roles and a potent antioxidant, with an ameliorative effect on spermatozoa. In the present study, the effect of melatonin on bovine spermatozoa was evaluated during in vitro sperm handling and under oxidative conditions in terms of sperm quality parameters and antioxidant capacity. Melatonin (100 μΜ) improved the kinematic parameters of spermatozoa, enhanced viability and reinforced the antioxidant status of spermatozoa by increasing cellular GSH levels and inhibiting iNOS protein expression.

There is an increasing interest in biomarkers of nitric oxide dysregulation and oxidative stress to guide management and identify new therapeutic targets in patients with chronic obstructive pulmonary disease (COPD). We conducted a systematic review and meta-analysis of the association between circulating metabolites within the arginine (arginine, citrulline, ornithine, asymmetric, ADMA, and symmetric, SDMA dimethylarginine), transsulfuration (methionine, homocysteine, and cysteine) and folic acid (folic acid, vitamin B6, and vitamin B12) metabolic pathways and COPD. We searched electronic databases from inception to 30 June 2023 and assessed the risk of bias and the certainty of evidence. In 21 eligible studies, compared to healthy controls, patients with stable COPD had significantly lower methionine (standardized mean difference, SMD=-0.50, 95% CI -0.95 to -0.05, p=0.029) and folic acid (SMD=-0.37, 95% CI -0.65 to -0.09, p=0.009), and higher homocysteine (SMD=0.78, 95% CI 0.48 to 1.07, p˂0.001) and cysteine concentrations (SMD=0.34, 95% CI 0.02 to 0.66, p=0.038). Additionally, COPD was associated with significantly higher ADMA (SMD=1.27, 95% CI 0.08 to 2.46, p=0.037), SDMA (SMD=3.94, 95% CI 0.79 to 7.08, p=0.014), and ornithine concentrations (SMD=0.67, 95% CI 0.13 to 1.22, p=0.015). In subgroup analysis, the SMD of homocysteine was significantly associated with the biological matrix assessed and the forced expiratory volume in the first second to forced vital capacity ratio, but not with age, study location, or analytical method used. Our study suggests the presence of significant alterations in metabolites within the arginine, transsulfuration, and folic acid pathways which can be useful for assessing nitric oxide dysregulation and oxidative stress and identifying novel treatment targets in COPD. (PROSPERO registration number: CRD42023448036)

Oxygen and hydrogen mobility are among the important characteristics for operation of solid oxide fuel cells, permselective membranes and many other electrochemical devices. This, along with other characteristics, enables reaching a high power density of solid oxide fuel cells and a high oxygen or hydrogen permeation fluxes for membranes. This work focuses on oxygen and hydrogen diffusion of mixed ionic (oxide ionic or/and protonic) – electronic conducting materials for these devices and its role in the performance. Ionic transport properties of conventional and state-of-the-art materials are reviewed.

The extensive use of engineered nanoparticles (ENPs) such as zinc oxide nanoparticles (ZnO NPs) in various commercial fields has spurred significant concern about its possible toxicological effects of ZnO NPs on human health and eco-system. Therefore, it is substantial to understand the aggregation phenomena which could attenuate this effect. This data article provides information on aggregation of ZnO NPs under the influence of various parameters of water chemistry. Moreover, Taguchi orthogonal array L27(313) design matrix was used to evaluate the effect of multiple parameters in aqueous solution. The data were obtained from single beam UV-Vis spectrophotometer (Optizen 2120 UV, Mecasys, Korea) using Optizenview 4.2.5 PC interference software, Fourier transform infrared spectrometer (FT/IR-4700, spectroscopy, JASCO Analytical Instruments, Easton, USA) and particle electrophoresis (NanoZS, Zetasizer, Malvern Instruments Ltd, Worcestershire, UK). The dataset draws attention on dominant parameters influencing aggregation of ZnO NPs in water. The analysis of variance (ANOVA) data revealed that electrolyte concentration, type and natural organic matter (NOM) concentration were the most significant parameters. Furthermore, FT-IR data presents a possible mechanism of ZnO NPs stabilization in the presence of different NOM. This data will be helpful for the development of environmental risk assessment strategies and prediction of fate and mobility of other ENPs in the aquatic environment.

Present worldwide difficulties in healthcare and the environment have motivated the investigation and research of novel materials in an effort to find novel techniques to address the current chal-lenges and requirements. In particular, the use of nanomaterials has demonstrated a significant promise in the fight against bacterial infections and the problem of antibiotic resistance. Metal na-noparticles and carbon-based nanomaterials in particular have been highlighted for their excep-tional abilities to inhibit many types of bacteria and pathogens. In order for these materials to be as effective as possible, synthetic techniques are crucial. Therefore, in this review article, we high-light some recent developments in the design and synthesis of various nanomaterials, including metal nanoparticles (e.g., Ag, Zn, or Cu), metal hybrid nanomaterials, and the synthesis of mul-ti-metallic hybrid nanostructured materials. Following that, examples of these materials’ applica-tions in antimicrobial performance targeted at eradicating multi-drug resistant bacteria, material protection such as microbiologically influenced corrosion (MIC), or additives in construction ma-terials have been described.

The aging mechanism of 10% and 30% nickel substituted manganese hexacyanoferrate cathode material in aqueous zinc-ion batteries has been explored through the advanced synchrotron-based two-dimensional x-ray fluorescence technique. Thanks to the two-dimension modality, not only the metal concentration dynamics throughout the entire electrodes was followed during the aging process, but their spatial distribution was also revealed, suggesting the route of the material transformation. The dissolution of Mn and Ni, and the penetration of Zn inside the framework, alongside the Mn aggregations outside the hexacyanoferrate framework were detected. Additionally, the possibility of conducting x-ray absorption spectroscopy measurements on the regions of interest made it possible to explore the chemical state of each metal, and furthermore, synchrotron-based powder x-ray diffraction demonstrated the gradual structural modification in 30% Ni-containing sample series, in terms of the different phase formation.