Three-dimensional porous nanostructures made of noble metals represent novel class of nanomaterials promising for nonlinear nanooptics and sensors. Such nanostructures are typically fabricated using either reproducible yet time-consuming and costly multi-step lithography protocols or less reproducible chemical synthesis that involve liquid processing with toxic compounds. Here, we combined scalable nanosecond-laser ablation with advanced engineering of the chemical composition of thin substrate-supported Au films to produce nanobumps containing multiple nanopores inside. Most of the nanopores hidden beneath the nanobump surface can be further uncapped using gentle etching of the nanobumps by an Ar-ion beam to form functional 3D plasmonic nanosponges. The nanopores 10-150~nm in diameter were found to appear via laser-induced explosive evaporation/boiling and coalescence of the randomly arranged nucleation sites formed by nitrogen-rich areas of the Au films. Density of the nanopores can be controlled by the amount of the nitrogen in the Au films regulated in the process of their magnetron sputtering assisted with nitrogen-containing discharge gas.

Residual stress (RS) is the most challenging problem in metal additive manufacturing (AM) since the build-up of high tensile RS may influence the fatigue life, corrosion resistance, crack initiation, and failure of the additively manufactured components. While tensile RS is inherent in all the AM processes, fast and accurate prediction of stress state within the part is extremely valuable and would result in optimization of the process parameters in achieving a desired RS and control of the build process. This paper proposes a physics-based analytical model to rapidly and accurately predict the RS within the additively manufactured part. In this model, a transient moving point heat source (HS) is utilized to determine the temperature field. Due to the high temperature gradient within the proximity of the melt pool area, material experience high thermal stress. Thermal stress is calculated by combining three sources of stresses known as stresses due to the body forces, normal tension, and hydrostatic stress in a homogeneous semi-infinite medium. The thermal stress determines the RS state within the part. Consequently, by taking the thermal stress history as an input, both the in-plane and out of plane RS distributions are found from incremental plasticity and kinematic hardening behavior of the metal by considering volume conservation in plastic deformation in coupling with the equilibrium and compatibility conditions. In this modeling, material properties are temperature-sensitive since the steep temperature gradient varies the properties significantly. Moreover, the energy needed for the solid-state phase transition is reflected by modifying the specific heat employing the latent heat of fusion. Furthermore, the multi-layer and multi-scan aspects of metal AM are considered by including the temperature history from previous layers and scans. Results from the analytical RS model presented excellent agreement with XRD measurements employed to determine the RS in the Ti-6Al-4V specimens.

A universally applicable method for the prediction of the isobaric heat capacities of the liquid and solid phase of molecules at 298.15 K is presented, derived from their “true” volume. The molecules’ “true” volume in A³ is calculated on the basis of their geometry-optimized structure and the Van-der-Waals radii of their constituting atoms by means of a fast numerical algorithm. Good linear correlations of the “true” volume of a large number of compounds encompassing all classes and sizes with their experimental liquid and solid heat capacities over a large range have been found, although noticeably distorted by intermolecular hydrogen-bond effects. To take account of these effects, the total amount of 1303 compounds with known experimental liquid heat capacities has been subdivided into three subsets consisting of 1102 hydroxy-group-free compounds, 164 monoalcohols/monoacids, and 36 polyalcohols/polyacids. The standard deviations for Cp(liq,298) were 20.7 J/mol/K for the OH-free compunds, 22.91 J/mol/K for the monoalcohols/monoacids and 16.03 J/mol/K for the polyols/polyacids. Analogously, 797 compounds with known solid heat capacities have been separated into a subset of 555 OH-free compounds, 123 monoalcohols/monoacids and 119 polyols/polyacids. The standard deviations for Cp(sol,298) were calculated to 23.14 J/mol/K for the first, 21.62 J/mol/K for the second, and 19.75 J/mol/K for the last subset. A discussion of structural and intermolecular effects influencing the heat capacities as well as of some special classes, in particular hydrocarbons, ionic liquids, siloxanes and metallocenes, has been given. In addition, the present method has successfully been extended to enable the prediction of the temperature dependence of the solid and liquid heat capacities in the range between 250 and 350 K.

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.

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.

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.

NiO-based nanomaterials have attracted a great deal of interest in view of various applications, that have stimulated the implementation of various synthetic approaches to control their chemico-physical properties as a function of the desired end-use. In this regard, their bottom-up preparation starting from suitable precursors plays an important role, but a molecular level in-sight into their reactivity remains an open challenge. In this study, we focus on the fragmentation of Ni(II) diketonate-diamine adducts, of interest as precursors for Ni(II) oxide systems, by com-bined electrospray ionization mass spectrometry (ESI-MS) with multiple collisional experiments (ESI-MSn) and theoretical calculations. The joint analyses revealed common features in the frag-mentation pattern of the target compounds: i) in the first-fragmentation, all three complexes form analogous base-peak cations by losing a negatively charged diketonate; in these cations, Ni-O and Ni-N interactions are stronger and the Ni positive charge is lower than in the neutral complexes; ii) the tendency of ligand electronic charge to migrate towards Ni further increases in the subsequent fragmentation processes, leading to the formation – in all three cases – of a tetracoordinated Ni environment involving an interesting cation-π intramolecular interaction.

Various iron oxides have been proven to be promising anode materials for metal-ion batteries due to their natural abundance, high theoretical capacity, ease of preparation, and environmental friendliness. However, the synthesis of iron oxide-based composites requires complex approaches, especially when it comes to composites with intrinsically conductive polymers. In this work we propose a one-step microplasma synthesis of a polyaniline-coated urchin-like FeOOH nanoparticles (FeOOH/PANI) for application as anode in lithium-ion batteries. The material shows excellent electrochemical characteristics, providing initial capacity of ca. 1600 mA∙h∙g−1 at 0.05 A∙g−1 and 900 mA∙g−1 at 1.2 A∙g−1. Further cycling lead to capacity decrease to 150 mA∙h∙g−1 by the 60th cycles, followed by a recovery that maintained the capacity at 767 mA∙h∙g−1 after 2000 cycles at 1.2 A∙g−1 and restored full initial capacity of 1600 mA∙h∙g−1 at low current density of 0.05 A∙g−1. Electrochemical milling of the material caused such interesting behavior of the material, and we confirmed this phenomenon by a combination of physico-chemical and electrochemical techniques. The anodes also exhibit high performance in a full cell with NMC532. NMC532//FeOOH/PANI full cell provided energy density of 224 Wh∙kg−1 which is comparable to the reference cell with graphite anode (264 Wh∙kg−1).

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.

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.

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.

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.

The combination of organic matter, iron oxide, and clay minerals is of great significance for the adsorption of copper ions (Cu). The purpose of this study is to explore the characteristics of Cu adsorption and laws governing Cu complexation to organic–inorganic, organic–clay mineral, and iron-oxide–clay mineral complexes in the sediments in the estuary of plateau fault and sinking lake——Dianchi Lake. In this study, Cu adsorption tests were performed on the three complexes, in order to study the kinetic behavior of adsorption, Langmuir and Freundlich isotherm models were used. The samples before and after adsorption were characterized via scanning electron microscope (SEM), Fourier infrared spectroscopy (FTIR), and X-ray diffraction (XRD). Our results show that, the Freundlich isotherm models model was able to describe adsorbent behavior in comparison to the Langmuir models. During the Cu adsorption process, the iron-oxide–clay mineral complex is able to adsorb Cu, via coordination exchange, through the –OH contained therein. Organic-matter–clay mineral complexes bonded to the surfaces of clay minerals by replacing the hydroxyl groups with functional groups (carboxyl groups or phenolic hydroxyl groups) contained in the organic matter. Organic–inorganic composites then adsorbed Cu through the coordination exchange of –OH in the polar functional groups of alcohols, phenols, and carboxylic acids. The adsorption capacity of Cu in these three sediment complexes was observed to have the following order: organic–inorganic complex > organic-matter–clay mineral complex > iron-oxide–clay mineral complex. The semi-quantitative analysis results of Fourier Infrared Spectroscopy show that the organic matter (changes in the peak area of functional groups such as carboxyl groups) in the organic-inorganic composite material has an important effect on the amount of copper ions adsorbed by clay minerals.

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.

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.

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.

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.

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.

Memristors are state-of-the-art, nano-sized, two-terminal, passive electronic elements with very good switching and memory characteristics. Owing to their very low power usage and a good compatibility to the existing CMOS ultra-high-density integrated circuits and chips, they are po-tentially applicable in artificial and spiking neural networks, memory arrays, and many other de-vices and circuits for artificial intelligence. In this paper, a complete electronic realization of ana-log circuit model of modified neural net with memristor-based synapses and transfer function with memristors and MOS transistors in LTSPICE is offered. Each synaptic weight is realized by only one memristor, providing enormously reduced circuit complexity. The summing and scaling implementation is founded on op-amps and memristors. The logarithmic-sigmoidal activation function is based on a simple scheme with MOS transistors and memristors. The functioning of the suggested memristor-based neural network for pulse input signals is evaluated both analytically in MATLAB-SIMULINK and in LTSPICE environment. The obtained results are compared one to another and are successfully verified. The realized memristor-based neural network is an im-portant step towards the forthcoming design of complex memristor-based neural networks for ar-tificial intelligence, for implementation in very high-density integrated circuits and chips.

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.

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.

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.

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.

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.

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.

The current economic development paradigm, which is based on steadily rising resource consumption and pollution emissions, is no longer viable in a world with limited resources and ecological capacity. The "green economy" idea has presented this context with a chance to alter how society handles the interplay between the environmental and economic spheres. The related concept of "green nanotechnology" aims to use nano-innovations within the fields of materials science and engineering to generate products and processes that are economically and ecologically sustainable, enabling society to establish and preserve a green economy. Many different economic sectors are anticipated to be impacted by these applications, including those related to corrosion inhibitor nano fertilizers, nano remediation, biodegradation, heavy metal detection, biofuel, insecticides & pesticides, and catalytic CO2 reduction. These innovations might make it possible to use non-traditional water sources safely and to create construction materials that are enabled by nanotechnology, improving living and ecological conditions. Therefore, our aim is to highlight how nanotechnology is being used in the green economy and to present promises for nano applications in this domain. Additionally, we want to critically examine the practical difficulties these applications raise, especially in consideration of any possible implications for the health and safety of those employed within this innovative sector. In the end, it emphasizes how critical it is to attain a really sustainable advancement in nanotechnology.

Metal complexes feature a wide range of available geometries, diversified lability, controllable hydrolytic stability, and easily available rich redox activity. These characteristics combined with the specific properties of the coordinated organic molecules result in many different mechanisms of biological action, making each of the myriads of the classes of metal coordination compounds unique. This focused review presents combined and systematized results of the studies of a group of copper(I) (pseudo)halide complexes with aromatic diimines and tris(aminomethyl)phosphines of a general formula [CuX(NN)PR₃], where X = I^- or NCS^-, NN = 2,2’-bipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline or 2,2’-biquinoline, and PR₃ = Air-stable tris(aminomethyl)phosphines. The structural and electronic properties of the phosphine ligands and luminescent complexes are discussed. The complexes with 2,9-dimethyl-1,10-phenanthroline, apart from being air- and water-stable, exhibit a very high in vitro antimicriobial activity against the Staphylococcus aureus and Candida albicans. Moreover, some of the complexes also show a strong in vitro antitumor activity against human ovarian carcinoma cell lines: MDAH 2774 and SCOV 3, CT26 (mouse colon carcinoma), and A549 (human lung adenocarcinoma) cell lines. The tested complexes are moderately able to induce DNA lesions through free radical processes, however the trends do not reflect observed differences in biological activity.

From 2020 to 2023 many people around the world were forced to wear masks for large proportions of the day based on mandates and laws. We aimed to study the potential of face masks for the content and release of inanimate toxins. A scoping review of 1003 studies was performed (database search in PubMed/MEDLINE, qualitative and quantitative evaluation). Twenty-four studies were included (experimental time 17 min to 15 days) evaluating content and/or release in 631 masks (273 surgical, 228 textile and 130 N95 masks). Most studies (63%) showed alarming results with high micro- and nanoplastics (MPs and NPs) release and exceedances could also be evidenced for volatile organic compounds (VOCs), xylene, acrolein, per-/polyfluoroalkyl substances (PFAS), phthalates (including di(2-ethylhexyl)-phthalate, DEHP) and for Pb, Cd, Co, Cu, Sb and TiO₂. Of course, masks filter bacteria, dirt and plastic particles and fibers from the air we breathe and have specific indications, but according to our data they also carry risks. Depending on the application, a risk-benefit analysis is necessary. However, mask mandates during the SARS-CoV-2 pandemic have been generating an additional source of potentially harmful exposition to toxins at population level with almost zero distance to the airways.

A variety of techniques have been utilized in metal additive manufacturing (AM) for melt pool size management, including modeling and feed-forward approaches. In a few cases, closed-loop control has been demonstrated. In this research, closed-loop melt pool size control for large-scale, laser-wire based Directed Energy Deposition is demonstrated with a novel modification: site-specific changes to the controller set-point were commanded at trigger points, the locations of which were generated by the projection of a secondary geometry onto the primary 3D-printed component geometry. The present work shows that, through this technique, it is possible to print a specific geometry that occurs beyond the actual toolpath of the print head. This is denoted as an extra-toolpath geometry and is fundamentally different from other methods of generating component features in metal AM. A proof-of-principle experiment is presented in which a complex oak leaf geometry was embossed on an otherwise ordinary double-bead wall made from Ti-6Al-4V. The process is introduced and characterized primarily from a controls perspective with reports on the performance of the control system, the melt pool size response, and the resulting geometry. The implications of this capability, which extend beyond localized control of bead geometry to the potential mitigations of defects and functional grading of component properties, are discussed.

The blue sepal color of hydrangea is due to a metal complex anthocyanin composed of 3-O-glucosyldelphinidin (1) and an aluminum ion with the co-pigments 5-O-caffeoylquinic acid (2) and/or 5-O-p-coumaroylquinic acid (3). The three components, namely, anthocyanin, Al³⁺ and 5-O-acylquinic acids, are essential for blue color development, but the complex is unstable and only exists in aqueous solution. Furthermore, the complex did not give analyzable NMR spectra or crystals. Therefore, many trials to determine the detailed chemical structure of the hydrangea-blue complex have failed to date. Instead, via experiments mixing 1, Al³⁺ and 2 or 3 in a buffered solution at pH 4.0, we obtained the same blue solution derived from the sepals. However, the ratio was not stoichiometric but fluctuated. To determine the composition of the complex, we tried direct observation of the molecular ion of the complex using electrospray-ionization mass spectrometry. In a very low-concentration buffer solution (2.0 mM) at pH 4.0, we reproduced the hydrangea-blue color by mixing 1, 2 and Al³⁺ in ratios of 1:1:1, 1:2:1 and 1:3:1. All solution gave the same molecular ion peak at m/z = 843, indicating that the blue solution has a ratio of 1:1:1 for the complex. By using 3, the observed mass number was m/z = 827 and the ratio of 1, 3 and Al³⁺ was also 1:1:1. A mixture of 1, 3-O-caffeoylquinic acid (4) and Al³⁺ did not give any blue color but instead was purple, and the intensity of the molecular ion peak at m/z = 843 was very low. These results strongly indicate that the hydrangea blue-complex is composed of a ratio of 1:1:1 for 1, Al³⁺ and 2 or 3.

Geothermal energy is a weather-independent, permanently available renewable energy source. In addition to producing heat and electricity, geothermal energy can be used to extract critical raw materials dissolved in the heat-carrying fluid. Researchers working on the frontiers of geothermal energy utilisation may be able to transform ultra-deep metallic mineral formations into “orebody-Enhanced Geothermal Systems”. In the planned technology, the metal-containing geological formation would be manipulated in such a way that cogeneration of energy and metals is possible and can be optimised in the future according to market needs. The potential of geothermal energy for sustainable mineral extraction and energy production aligns with Sustainable Development Goal (SDG) 7, which aims to ensure access to affordable, reliable, sustainable, and modern energy for all. This new technology could substantially decrease Europe’s dependency on importing critical metallic minerals (such as lithium and tungsten) and energy; over and above, it has a small environmental footprint, including very low carbon emissions

Fine chemicals are produced in small annual volume batch processes (often <10,000 tonnes per year), with a high associated price (usually > $10/kg). As a result of their usage in the production of speciality chemicals, in areas including agrochemicals, fragrances and pharmaceuticals, their necessity will remain high for the foreseeable future. This review article assesses current methods used to produce fine chemicals with heterogeneous catalysts, including both well-established methods as well as newer experimental methods. A wide range of methods utilising microporous and mesoporous catalysts has been explored, including their preparation and modification before use in industry. Their potential drawbacks, as well as benefits, have been analysed, with their feasibility compared to newer, recently emerging catalysts. The field of heterogeneous catalysis for fine chemical production is a dynamic and ever-changing area of research. This deeper insight into catalytic behaviour and material properties will produce more efficient, selective, and sustainable processes in the fine chemical industry. The findings from this article will provide an excellent foundation for further exploration and a critical review in this field of fine chemical production using micro- and mesoporous heterogeneous catalysts.

Structure and reversibility of cross-link junctions play pivotal roles in deter- mining the nature of thermoreversible gelation and dynamic mechanical prop- erties of the produced polymer networks. We attempt to explore new types of sol–gel transitions with mechanical sharpness by allowing cross-links to grow without upper bound. We consider thermoreversible gelation of the primary molecules R{Af} carrying the number f of low molecular weight functional groups (gelators) A. Gelators A are assumed to form supramolecular assemblies. Some examples are: telechelic polymers (f = 2) carrying π–π stacking benzene derivatives at their both ends, trifunctional star molecules (f = 3) bearing mul- tiple hydrogen-bonding gelators. The sol–gel transition of the primary molecules becomes sharper with the cooperativity parameter of the stepwise linear growth of the cross-links. There is a polymerization transition (crossover without singu- larity) of the junctions in the postgel region after the gel point is passed. If the gelator A tends to form supramolecular rings competitively with linear chains, there is another phase transition in the deep postgel region where the average molecular weight of the rings becomes infinite (Bose-Einstein condensation of rings). As a typical example of binary cross-links where gelators A and B form mixed junctions, we specifically consider metal-coordinated binding of ligands A by metal ions B. Two types of multi-nuclear supramolecular complexes are studied: (i) linear stacking (ladder) of the sandwich A2B units, (ii) linear train of egg-box A4B units. The average molecular weight, the gel fraction, the av- erage length of the cross-link junctions are calculated for all of these models as functions of the functionality f, the concentration of the solute molecules, and temperature. Potential candidates for the realization of these new types of thermoreversible gelation are discussed.

This study presents the encapsulation of two amino acid-based ionic liquids (AAILs), 1-Ethyl-3-methylimidazolium glycine [Emim][Gly] and 1-Ethyl-3-methylimidazolium alanine [Emim][Ala], in a highly porous metal organic framework (MOF-177), to generate state-of-the-art composites for post-combustion CO2 capture. The thermogravimetric analysis (TGA) demonstrated a successful encapsulation of the AAILs, consequently dramatically reducing the composites' surface area and pore volume. Both [Emim] [Gly]@MOF-177 and [Emim][Ala]@MOF-177 had close to 3 times the CO2 uptake of MOF-177 at 20 wt.% loading, 0.2 bar, and 303 K. Additionally, 20-[Emim][Gly]@MOF-177 and 20-[Emim] [Ala]@MOF-177 enhanced their CO2/N2 selectivity from 5 (pristine MOF-177) to 13 and 11, respectively.

Interviews from strength and conditioning coaches across all levels of athletic competition identified their two biggest concerns with the current state of wearable technology: (a) the lack of solutions that accurately capture data "from the ground up" and (b) the lack of trust due to inconsistent measurements. The purpose of this research is to investigate the use of liquid metal sensors, specifically Liquid Wire sensors, as a potential solution for accurately capturing ankle complex movements such as plantar flexion, dorsiflexion, inversion, and eversion. Sensor stretch linearity was validated using a Micro-Ohm Meter and a Wheatstone bridge circuit. Sensors made from different substrates were also tested and discovered to be linear at multiple temperatures. An ankle complex model and computing unit for measuring resistance values were developed to determine sensor output based on simulated plantar flexion movement. The sensors were found to have a significant relationship between the positional change and the resistance values for plantar flexion movement. The results of the study ultimately confirm the researchers' hypothesis that liquid metal sensors, and Liquid Wire sensors specifically, can serve as a mitigating substitute for inertial measurement unit (IMU) based solutions that attempt to capture specific joint angles and movements.

The broad acceptance of electromobility depends heavily on the performance and service life of the battery technology used. Lithium-ion battery technology is currently the most promising energy storage technology for mobile applications, but the performance and capacity of the cells is extremely temperature sensitive. Especially in these new complex and powerful applications there is a significant need for thermal management. Depending on the ambient conditions, part of the effective battery energy must therefore be used to temper the system. So far, mainly active components have been used for this task. This not only reduces the overall efficiency, but also increases the weight, volume and maintenance requirements of the system. In the present work, an alternative battery temperature management system (BTMS) was developed. A concept based on latent heat storage materials was created, which uses the advantages of thermal energy storage and the design freedom of additive manufacturing technology, and its suitability for use in battery applications was checked. On the one hand, the use of systems for storing thermal energy was researched and, on the other hand, an innovative cooling concept was created considering new production possibilities.

The article focuses on the galvanic replacement synthesis of Ti-Ni and Zr-Ni metal systems with the "core-shell" structure which are potential precursors for intermetallics. The authors defined the effective synthesis parameters and the formation features of polymetallic systems character-ized by granulometric, phase and elemental composition. The X-ray fluorescence and X-ray phase analysis methods showed that the deposition of nickel on dispersed titanium and zirconium leads to the production of test samples with phase composition representing a mechanical mixture of Ni and Ti, Ni and Zr. The method of X-ray fluorescence analysis showed that the presence of hy-drofluoric acid with a 0.5-1.5 M concentration results in the formation of fixed quantitative ratios of elements in the precipitate, which allows the quantitative composition of dispersed systems "titanium - nickel", "zirconium - nickel" to be regulated within a relatively wide range. Scanning electron microscopy proved that all synthesized systems are characterized by a highly porous structure that follows the titanium and zirconium particle surface contour and the presence of spherical nanoscale subunits on the formed particle surface.

While traditional AC mechanical circuit breakers have been competent for protecting AC circuits, high penetration of DC power distribution technologies like DC microgrids (MGs) obligate better disruption performance features such as quick and reliable switch-ing speeds. However, a DC circuit breaker (DCCB) novel design is challenging due to the need to quickly break high currents within milliseconds, caused by the high fault current rise in DC grids compared to AC grids. In DC grids, the circuit breaker must provide zero current crossing and be designed for absorbing surges since the arc is not naturally extinguished by the system. Additionally, the DC breaker must mitigate the magnetic energy stored in the system inductance and withstand residual over-voltages after current interruption. These challenges require a fundamentally different topology for DCCBs, which are typically made using solid-state semiconductor technology, metal oxide varistors (MOV), and ultra-fast switches. This study aims to provide a comprehensive review on development, design, and performance description of DCCBs in parallel with a specific concentration on analysis of internal topology, energy absorption path and sub-circuits in Solid-State (SS)-based DCCBs. The research explores various novel designs that introduce different structures for energy dissipation solution. The classification of these designs is based on the fundamental principles of surge mitigation and a detailed analysis of the techniques employed in DCCBs. In addition, our framework offers an advantageous reference point for the future evolution of SS-circuit breakers in numerous developing power delivery systems.

The dynamic behaviour of a machine tool (MT) directly influences the machining performances. The adoption of lightweight structures may reduce the effects of undesired vibrations and increasing the workpiece quality. This paper aims to present and compare a set of hybrid materials that may be excellent candidate to fabricate the MT moving parts. The selected materials have high dynamic characteristics and capacity to damp mechanical vibrations. In this way, starting by the kinematic model of a milling machine that highlights the main critical factors, this study paper evaluates a number of prototypes made of Al Foam sandwiches (AFS), Al Corrugated sandwiches (ACS) and materials reinforced by carbon fibres (CFRP). A set of prototypes has been fabricated, represented the Z-axis ram of a commercial milling machine. The static and dynamical properties have been evaluated by using both FE simulations and experimental tests. The obtained results show that the proposed structures may be a valid alternative to the conventional materials of MT moving parts, increasing machining performances. In particular, the AFS prototype highlighted a damping coefficient that is 20 times greater than a conventional ram (e.g. steel). The CFRP structure is able to satisfy the machining requirements with a reduced weight of 48.5%, while the ACS prototype showed a good trade-off between stiffness and damping.

We delve into the axion-dilaton model within the supergravity framework, with a specific focus on the intricacies of domain wall construction and stability. Employing holographic vitrification, we unravel the dynamics of domain wall formation in gauge theories featuring periodic vacuum structures. Our model, incorporating a QCD-like axion term and a stabilizing dilaton, undergoes scrutiny for conductivity variations under weak disorder. The investigation reveals the model's resilience, manifesting near-perfect conductivity under mild disorder conditions. However, the rigorous mathematical motivation for the holographic setup demands further elucidation. The scattered nature of our results prompts the necessity for a more systematic interpretation of QCD phenomena and conductivity transitions. This study contributes to the mathematical understanding of the axion-dilaton model's behavior, highlighting the imperative for a refined holographic framework and a more coherent interpretation of observed phenomena.

This paper investigates if the polar groups induced by a plasma treatment can increase the lap shear strength of laser joined metal and plastic hybrids. Optimal laser joining parameters for cold-rolled AISI304 – Polyamide 6.6 and sandblasted AISI304 - Polypropylene hybrids are developed. The OWRK-method was utilized to identify the change in surface free energy of a low-pressure plasma treatment. Plasma treated samples were joined and tested. The fractured surfaces were investigated via light microscopy and SEM. The arithmetic means of the plasma treated hybrids lap shear strength with polyamide 6.6 varied slightly but all measured values were within the range of the untreated samples. The lap shear strengths of the polypropylene hybrids were significantly reduced. This was attributed to an overaging and the development of low molecular weight oxidized materials which lead to a weak boundary layer. No correlation between surface free energy and the lap shear strength could be found.

This study describes all the properties of high T_c cuprates by introducing rotating holes that are created by angular momentum conservations on a 2D CuO₂ surface, and which have a different mass from that of a normal hole because of the magnetic field energy induced by the rotation. This new particle called a macroscopic Boson describes the doping dependences of pseudo-gap temperature and the transition temperature at which an anomaly metal phase appears and describes the origin of the pseudo-gap. Furthermore, this study introduces a new model to handle many-body interactions, which results in a new statistic equation. This statistic equation describing many-body interactions accurately explains why high T_c cuprates have significantly high critical temperatures. Moreover a partition function of macroscopic Bosons describes all the properties of anomaly metal phase, which sufficiently agree with experiments, using the result from our previous study [1] that analytically describes the doping dependence of T_c. By introducing a macroscopic Boson and the new statistical model for many-body interactions, this study uncovered the mystery of high T_c cuprates, which have been a challenge for many researchers. An important point is that, in this study, pure analytical calculations are consistently conducted, which agree with experimental data well (i.e., they do not use numerical calculations or fitting methods but use many actual physical constants).

To date, theoretical analyses have provided several useful methods/algorithms for studying transition states and non-covalent interactions. Potential Energy Scan (PES) is one such method that has found wide application in the physicochemical community. Analyzing the PES profiles of the catalytic system of FeBr3 in Electrophilic Aromatic Substitution (EAS) with molecular halogens, one can notice an obvious difference from the modern textbook mechanisms proposed in this area of study. Moreover, the newly presented Graphic Methodology (GM) allows a simple and reliable transition state determination even for very weakly bound charge transfer complexes using second-order derivatives as an efficient tool in the graphical analysis. Relative errors that can be reduced to a few parts per thousand in transition state estimation make this method a potentially very useful tool in further graphical studies of non-covalent interactions. Studies performed using high-precision semiempirical methods suggest that the process of halonium ion quenching proceeds along a completely different pathway, suggesting a possible novel transition metal-nonmetal catalytic system involved in the EAS electrophilic quenching step. The results presented here strongly suggest a future GM application that is widely used and the introduction of pseudo and pre-transition states as new terms in the description of non-covalent interactions.

In this paper, the overall performance of Cu-(In,Ga)-Se₂ (CIGSe) solar cells was improved in the ultraviolet (UV)–visible wavelength region by two-segment process. In which, adjusting DC sputtering powers (20–40 W) for absorbers (segment I), and metal-alloy compositions (CdS, ZnO/CdS, ZnMgO/CdS and ZnMgO) for buffers (segment II) were explored and characterized. Upon choosing the optimal-30-W CIGSe-absorber (with 0.95-CGI ratio) sputtered by the segment-I process, the Cu-rich film can distinctly boost grain growth, thus reducing the trap state density. After segment-II process as the toxic-CdS alternative, the optimal Zn_0.9Mg_0.1O-alloy buffer can reach the best conversion efficiency (η = 8.70%) was attained for the environmental protection. Meanwhile, and the overall internal/external quantum efficiencies (IQE/EQE) were improved by 13.15%, respectively for the 2.48–3.62-eV bandgap (short wavelength) range. The developed photovoltaic (PV) module (with 9 optimum-CIGSe cells) exhibits acceptable stability with a variance within ±5% over the 60-day experiment. This discovery in PV-device research contributes to a new scientific understanding of renewable energy. Furthermore, this study undeniably enhances the progress of practical applications for PV-modules in alignment with sustainable development goals. It also actively supports the development of eco-friendly communities.

Short-range Internet of Things (IoT) sensor nodes operating at 2.4 GHz need to provide ubiquitous wireless sensor networks (WSNs) with energy-efficient, wide-range output power (POUT) and fully integrated on a single chip for wireless body area networks (WBANs) and wireless personal area networks (WPANs) using low-power Bluetooth (BLE) and Zigbee standards. The proposed fully integrated transmitter (TX) utilizes a digitally controllable current-mode class-D (CMCD) power amplifier (PA) with a second harmonic distortion (HD2) suppression to reduce VCO pulling in an integrated system while meeting harmonic limit regulations. The CMCD PA is divided into 7-bit slices that can be reconfigured between differential and single-ended topologies. Duty cycle distortion compensation is performed for HD2 suppression, and an HD2 rejection filter and a modified C-L-C low-pass filter (LPF) reduce HD2 further. Implemented in a 28 nm CMOS process, the TX achieves a wide POUT range of from 12.1 to -31 dBm and provides a maximum efficiency of 39.8% while consuming 41.1 mW at 12.1 dBm POUT. The calibrated HD2 level is -82.2 dBc at 9.93 dBm POUT, resulting in a transmitter figure of merit (TX_FoM) of -97.52 dB. Higher order harmonic levels remain below -41.2 dBm even at 12.1 dBm POUT, meeting regulatory requirements.