Nanomaterials based on metal oxides (MexOy) are employed as catalysts and/or sorbents in processes undergoing conditions in supercritical water (scH2O), the “green” reaction medium used to obtain energy relevant products. Their properties are greatly affected by the synthesis method used to produce the active MexOy. Moreover, in order to maintain their performance, it is more practical and cost-effective to use supported MexOy nanoparticles. Within this context, the present work deals with the preparation of carbon-supported ZnO and CuO composites by an innovative method based on impregnation under scH2O conditions. Metal oxides were impregnated on a carbon (C) support using a continuous flow tubular reactor. The results show that impregnation in scH2O is a promising approach for the preparation of ZnO/C and CuO/C composite materials. This one-step synthesis method, in a continuous flow, uses neither seed layer nor mineralizer, and it needs substantially lower preparation times than the conventional impregnation methods.

Free-Living Amoebae (FLA) are widely distributed protozoa in both nature and artificial environments such as drinking water. Besides the ability of all FLA to transport various pathogenic microorganisms, certain species, Acanthamoeba spp. or Balamuthia mandrillaris, have intrinsic pathogenic abilities and cause severe cerebral infections. Previous work has shown an enrichment of FLA cysts in biofilm developed in upper levels of Drinking Water Storage Towers (DWST), suggesting that differences in densities of FLA cysts may play a role in their unequal distribution in the water column. To evaluate this hypothesis, a model of a water column was created for this study and used to analyze the vertical distribution of cysts of the FLA Acanthamoeba castellanii, Vermamoeba vermiformis and Balamuthia mandrillaris from 0 to 23 weeks. Interestingly, our data showed that the cysts of both A. castellanii and V. vermiformis were enriched in upper water levels during their aging. However, B. mandrillaris cysts were equally distributed in the water column during the entire study. These results showed that, besides the role of the water level variation in the DWST, some FLA cysts can become less dense during their aging, which contributes to their enrichment in upper water, and thus biofilm levels.

Deep eutectic solvents are a mixture of two or more components, that at a particular composition become liquids at room temperature. When the compounds that constitute the DES are primary metabolites, namely, amino acids, organic acids, sugars, or choline derivatives, the DES are so called natural deep eutectic solvents (NADES). NADES fully represent green chemistry principles. These solvents are highly welcome, as they are obtained from renewable resources, and gratifyingly biodegradable and biocompatible. They are an alternative to room temperature ionic liquids (RTILs). From the pharmaceutical industry point of view, they are highly desirable, but unfortunately have been rarely used despite their enormous potential. In this review, we will look at their impact on the asymmetric catalytic synthesis of key target molecules, via metal-based catalysis, biocatalysis and organocatalysis. In many cases the NADES that have been used are chiral and can even promote enantioselective reactions, this crucial and very exciting aspect will also be discussed and analysed.

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 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.

How Nature discovered genetic coding is a largely ignored question, yet the answer is key to explaining the transition from biochemical building blocks to life. Other, related puzzles also fall inside the aegis enclosing the codes themselves. The peptide bond is unstable with respect to hydrolysis. So, it requires some form of chemical free energy to drive it. Amino acid activation and acyl-transfer are also slow and call for catalysis. All living things must thus also convert free energy and synchronize cellular chemistry. Most importantly, functional proteins occupy only small, isolated regions of sequence space. Nature evolved heritable symbolic data processing to seek out and use those sequences. That system has three parts: a memory of how amino acids behave in solution and inside proteins, a set of code-keys to access that memory, and a scoring function. The code-keys themselves are the genes for cognate pairs of tRNA and aminoacyl-tRNA synthetases, AARS. I outline the surprising links between all these questions and the structural duality of the base-pairing that holds genes together and how those links arise from the experiments.

Novel Ca3(BTC)2 metal-organic frameworks with different sizes and shapes constructed by Ca2+ and trimesic acid as metal center and ligands respectively were synthesized by a surfactant-assisted method. The relationship between the quantity of surfactant and the particle morphology of the product have been further studied. The samples were characterized by scanning electron microscope, powder X-ray diffraction and Inductively coupled plasma mass spectrometry. The results indicated that the size and shape of Ca3(BTC)2 could be regulated by changing the quantity of surfactant. Rod- and sheet-like Ca3(BTC)2 MOFs have been readily availabled. The removal kinetics of heavy metals of Pb(II) were also studied by rod-like Ca3(BTC)2. The results showed that as-synthesized Ca3(BTC)2 could effectively remove heavy metals of Pb(II) from the sewage.

Urban gardens have important social, environmental and economic roles in big cities, contributing to their sustainability. However, food production in urban gardens may be compromised due to soil pollution that resulted from decades of industrial non-regulated environmental activity and mobile transport. In this study, 12 soils from the urban agricultural area of Rome (Italy) were analyzed for the metals Be, Ba, Pb, Co, Ni, V, Zn, Hg, Cd, As, Cu, and Cr. All but one of the soils under analysis were characterized by at least one metal concentration above the threshold limit defined by the Italian Legislative Decree 152/2006 (ILD) for agricultural soils. Multivariate analysis showed that the soils could be classified into five clusters: clusters I and II had relatively lower mean metal concentrations; clusters III, IV, and V had relatively higher mean metal concentrations with several metal concentrations above the threshold proposed by ILD. Three factors contributing to the variability of the metal’s concentration in the soils under investigation were identified: geological factor, related with metals As, Ba, Be, and V; anthropogenic factor, related with Pb and Cu; and, a mixed factor related with Co, Cr, Ni, and Zn. High metal content may limit the utilization of urban soils as urban gardens for food production.

This manuscript employs a surface stress-driven nonlocal model to explore the combined effects of long-range interaction and surface energy on higher vibration modes of functionally graded nanobeams. The nanobeam theory, based on Bernoulli-Euler kinematics, incorporates surface effects such as surface elasticity, surface residual stresses, surface density, and rotary inertia. Hamilton's principle is applied to derive the governing equation with size-dependent considerations. The main outcomes of a parametric investigation, considering four different kinematic boundary conditions (Cantilever, Simply-Supported, Clamped-Pinned, and Doubly-Clamped) while varying the nonlocal parameter and material gradient index, are presented and discussed. Additionally, the normalized natural frequencies for the second, third, fourth and fifth modes of vibrations are provided and analyzed for each case under study. The results underscore the model's effectiveness in capturing surface energy effects on the overall dynamic behavior of functionally graded Bernoulli-Euler nanobeams, offering a cost-effective approach for designing and optimizing nano-scaled structures.

Space–air–ground integrated network (SAGIN) is considered as an enabler for the sixth-generation (6G) networks. By integrating terrestrial and non-terrestrial (satellite, aerial) networks, SAGIN seem to be a quite promising solution to provide reliable connectivity everywhere and all the time. Their availability can be further enhanced if hybrid free space optical (FSO)/radio frequency (RF) links are adopted. In this paper, the performance of a hybrid FSO/RF communication system operating in SAGIN has been analytically evaluated. In the considered system, a high altitude platform station (HAPS) is used to forward the satellite signal to the ground station. Moreover, the FSO channel model assumed takes into account the turbulence, pointing errors and path losses, while for the RF links, a relatively new composite fading model has been considered. In this context, a new link selection scheme has been proposed that is designed to reduced the signaling overhead required for the switching operations between the RF and FSO links. The analytical framework that has been developed is based on the Markov chain theory. Capitalizing on this framework, the performance of the system has been investigated using the criteria of outage probability and the average number of link estimations. The numerical results presented reveal that the new selection scheme offers a good compromise between performance and complexity.

The influence of applied loads on free vibrations analysis of plates and shells panels made of functionally graded materials is analyzed in the present work. Formulations for the static analysis considering geometrically nonlinear behavior, as well as linear buckling and free vibrations analyses are considered. The calculation of the through-thickness stress distribution is also performed. A finite element model based on a higher order shear deformation theory and using a non-conforming triangular flat plate/shell element with 3 nodes, and 8 degrees of freedom per node is used in the numerical implementation. The results obtained with this numerical model are presented, discussed, and compared with alternative solutions published by other authors in some benchmark applications.

The aim of the study was to determine the occurrence and characteristics of coagulase-positive Staphylococcus strains in the carcasses of wild birds and aviary capercaillies in south-eastern Poland. Samples from capercaillies and wild birds belonging to 12 orders and 26 species were tested. The resistance of the strains and the presence of selected virulence genes were examined. Similarity analysis of the isolates was performed using pulsed-field gel electrophoresis (PFGE). Coagulase-positive Staphylococcus strains accounted for 5.7% and belonged to the species: Staphylococcus aureus, Staphylococcus pseudintermedius and Staphylococcus delphini. Among isolated strains, 15.8% were multidrug resistant. The most frequently detected virulence genes were hla in 58% of isolates and hlb and hld in 47.4% of isolates., The results of multiplex PCR showed the presence of genes responsible for the production of enterotoxins C, B, E, and J, in single isolates. It can be concluded that coagulase-positive Staphylococcus strains accounted for a small percentage of staphylococci isolated from free-living birds in the study area. The occurrence of multidrug-resistant coagulase-positive Staphylococcus strains in aviary capercaillies suggests that they play a role in the transmission and spread of resistant strains into the environment. Free-living birds may be also a significant reservoir of enterotoxigenic Staphylococcus strains.

Heavy metal pollution poses a significant threat to global populations, particularly impacting human health. Developing countries, characterized by chemical engineering and mining industrial activities, often contribute to diverse heavy metal contaminants. Consumption of water contaminated with heavy metals, prevalent in such regions, can lead to severe health risks, including gastric cancer. Addressing the urgent issue of heavy metal pollution, this paper employs a bibliographic approach to explore the latest literature on heavy metal pollution. The study discusses recent research findings and potential methods for the treatment and mitigation of heavy metal pollution, emphasizing the pressing need for effective solutions to safeguard public health.

Along time, many minted coins were withdrawn from circulation, being replaced with new ones. The returned obsolete metal coins were melted in order to sustainable reuse of the alloy for other purpose. Between the withdrawing and melting, some of the metal coins were cancelled by destruction of the original shape and dimension, using some adequate tools. In the first part, the paper is focused to present some aspects insight of the cancelling method used on the Romanian old nickel coins; also, there are presented some examples. The introductive part also includes the literature review in the field of coin manufacturing, covering the subjects as metal behavior under the striking load, aspects about the 3D modeling and FEM analysis or explaining some striking errors. Result the paper main purpose, to study the particularities of one or another cancelling method applied on subjected coins, which conducted to more or less valuable collection metal pieces. In the paper second part, is introduced the adequate 3D model, computed for the cancelling dies, respectively the coin. Then, there are introduced the assembled models, corresponding to each cancelling case, which consist by the obverse and reverse cancelling dies, having the coin inside them. For the each model, the finite element analysis is realized and is achieved for different initial conditions. The final part of the paper presents the analysis results and also the discussions and conclusions.

Recent developments in the field of room temperature ferromagnetic metal oxide semiconductors (RTFMOS) have shown promising potential for improved photocatalytic performance. This review focuses on the combined study of photocatalytic and ferromagnetic properties at room temperature, with a particular emphasis on metal oxides, such as TiO2, which have emerged as a key area of interest in the domains of magnetism and environmental remediation. Despite extensive research over the years, the precise mechanism behind the interplay of ferromagnetism and photocatalysis in these materials remains incompletely understood. Several critical factors contributing to magnetism have been hinted at, including oxygen vacancies and various metal doping. Numerous reports have demonstrated that these factors play a primary role in room temperature ferromagnetism and photocatalysis in wide-band-gap metal oxides. However, establishing a direct correlation between magnetism, oxygen vacancies, dopant concentration, and photocatalysis has proven challenging. This review aims to provide a comprehensive overview of the recent progress in understanding the magnetism and photocatalytic behaviour of metal oxides. By examining the latest findings, this study sheds light on the potential of RTFMOS as effective photocatalysts, thereby contributing to advancements in environmental remediation and related applications.

De-escalation is currently taking place both in surgical and systemic treatment of breast cancer. The introduction of trastuzumab, the first monoclonal antibody against the HER2 receptor over 20 years ago was a milestone in the treatment of HER2 positive breast cancer and marked the beginning of a new era in targeted tumor therapy. In the sense of de-escalation, omitting non-targeted cytotoxic chemotherapy altogether is often hailed as the ultimate goal of oncological research. Especially in case of small, node-negative, HER2 positive early breast cancer, it remains a challenge for clinicians to establish the safest and most efficient treatment plan while considering the significant potential for toxic side effects associated with chemotherapy and HER2 targeted therapy, and the generally excellent prognosis. In this context, several ongoing studies are currently assessing chemotherapy-free regimens as part of strategies aimed at de-escalating therapy in the field of HER2 positive early breast cancer. Despite promising early results from these studies, combination of anti-HER2 treatment with chemotherapy backbone remains standard of care.

Graphene materials synthesized using direct laser writing (laser-induced graphene; LIG) are fa-vorable sensor materials because of their large surface area, ease of fabrication, and cost effec-tiveness. In particular, LIG decorated with metal nanoparticles (NPs) has been used in various sensors, including chemical sensors and electronic and electrochemical biosensors. However, the effect of metal decoration on LIG sensors remains controversial; hypotheses based on computa-tional simulations do not always match experimental results, and even experimental results re-ported by different researchers have not been consistent. In the present study, we explored the effects of metal decorations on LIG gas sensors, with NO2 and NH3 gases as representative oxi-dizing and reducing agents, respectively. To eliminate unwanted side effects arising from metal salt residues, metal NPs were directly deposited by vacuum evaporation. Although the gas sen-sitivities of the sensors deteriorate upon metal decoration irrespective of the metal work function in the case of NO2 gas, they improve upon metal decoration in the case of NH3 exposure. A careful investigation of the chemical structure and morphology of the metal NPs in the LIG sensors shows that the spontaneous oxidation of metal NPs with a low work function changes the be-havior of the LIG gas sensors and that the sensor behaviors under NO2 and NH3 gases follow different principles.

Usually, the vector control of the induction machine (IM) is done by using cascade control structures with conventional linear PI controllers, the inner loop being designed for current control, and the outer loop for rotor flux and speed control. In this paper, starting from the dq model of the IM with the rotor magnetic flux space vector aligned along the d axis, advanced control algorithms are proposed for the two control loops of the cascade structure. For the current inner loop, after the decoupling control of the two dq currents, predictive algorithms with constraints are used to control and limit the currents. Since the outer loop has a nonlinear affine multivariable plant model, a homotopy-based variant of feedback linearization is used to obtain a non-singular decoupling matrix of the feedback transformation even when the rotor flux is zero at the start-up of the motor. During the continuous variation of the homotopy parameter, the model of the plant is variable, in which case the model free algorithms are properly used to control the flux and speed of the IM. The comparative analysis obtained for the cascade structure with conventional PI controllers and advanced algorithms, respectively, shows that the last lead to improve the dynamical performance of the IM.

Amid the deepening imbalance in the supply and demand of allogeneic organs, xenotransplanta-tion can be a practical alternative because it makes an unlimited supply of organs possible. How-ever, to perform xenotransplantation on patients, the source animals to be used must be free from infectious agents. This requires breeding of animals using assisted reproductive techniques, such as somatic cell nuclear transfer, embryo transfer, and cesarean-section, without colostrum de-rived in designated pathogen-free (DPF) facilities. Most infectious agents can be removed from animals produced by these methods, but several viruses known to pass through the placenta are not easy to remove, even with these methods. Therefore, in this review, we look at the characteris-tics of several viruses known to cross the placenta and determine how they can be detected. This review is intended to help maintain DPF facilities by preventing animals infected with the virus from entering DPF facilities and to help select pigs suitable for xenotransplantation.

Prostate cancer (PC) is the second most diagnosed cancer among men. It was observed that early diagnosis of disease is highly beneficial for survival of cancer patients. Therefore, extension and increasing quality of life of PC patients can be achieved by broadening the Cancer Screening programs that are aimed at the identification of cancer manifestation in patients at earlier stages before they demonstrate well-understood signs of the disease. Therefore, there is an urgent need in standard, sensitive, robust, and commonly available screening and diagnosis tools for identification of early signs of cancer pathologies. In this respect, “Holy Grail” of cancer researchers and bioengineers for decades have been molecular sensing probes that would allow diagnosis, prognosis, and monitoring of cancer diseases by their interaction with cell-secreted and cellassociated PC biomarkers, e.g. PSA and PSMA correspondinly. At present, most PSA tests are performed at centralized laboratories using high throughput Total PSA immune analyzers which are suitable for dedicated laboratories and are not readily available for the broad health screening. Therefore, the current trend in detection of PC is developments of the portable biosensors for mobile laboratories and individual use. Phage display since its conception by George Smith in 1985 has emerged as a premier tool in molecular biology with widespread applications. This review describes how the paradigm of molecular evolution and phage display revolutionized the methods of early diagnosis and monitoring of PC.

The incidence of celiac disease and gluten intolerance has been significantly rising globally. Gluten-free product consumption registered a sudden rise also among tolerant people, due to psychosocial factors. Biscuits are popular, low-cost bakery foods, consumed by nearly everyone worldwide. The removal of gluten from the baked product causes some undesirable traits and different textures and tastes. The main goal consists of creating a food product with the same taste and texture as a product with gluten. Moreover, gluten-free bakery products are usually low-grade sources of protein and poor in dietary fiber. Quinoa is a source of TDF and valuable protein. In this study, quinoa flour was used as the main constituent in the formulation of gluten-free c to improve their nutritional properties. Six different recipes with different percentages of quinoa flour have been realized. The formulations were compared, by rheological analysis, of each other and with a wheat flour control shortbread. The recipes with rheological features more similar to control shortbread were subjected to a discrimination analysis and the preferred was characterized from a chemical-physical and sensorial point of view. The experimental shortbreads constituted a good compromise to exploit the good nutritional composition of quinoa maintaining an acceptable sensory profile.

The retrospective noninterventional study investigated the kinetic energy of video images of 18 fertilized eggs (7 were normal and 11 were abnormal) recorded by a time-lapse device leading up to the beginning of the first cleavage. The norm values of cytoplasmic particles were measured by the optical flow method. Three phases profile for normal cases were found regarding the kinetic energy that were 2.199×10⁻²⁴±2.076×10⁻²⁴, 2.369×10⁻²⁴±1.255×10⁻²⁴, and 1.078×10⁻²⁴±4.720×10⁻²⁵ (J) for the phases 1, 2, and 3, respectively. In phase 2, the energies were 2.369 × 10⁻²⁴ ± 1.255 × 10⁻²⁴ and 4.694 × 10⁻²⁴ ± 2.996 × 10⁻²⁴ (J) (mean ± SD, P = 0.0372), and the time required was 8.114 ± 2.937 and 6.018 ± 5.685 (H) (P = 0.0413) for the normal and abnormal cases, respectively. The kinetic energy change was considered a condition for applying the free energy principle that states that, for any self-organized system to be in equilibrium in its environment, it must minimize its informational free energy. The kinetic energy while interpreting it in terms of the free energy principle suggesting clinical usefulness would further our understanding of the phenomenon of fertilized egg development with respect to the birth of human life.

Biofilm serves as the residence for bacteria, wherein bacteria attach to surfaces and produce extracellular polymeric substances, including proteins, polysaccharides, and extracellular DNA. In recent years, biofilm reactors have gained increasing significance, playing a crucial role, for instance, in immobilizing heavy metals from waterways. This paper employs a bibliographic study to analyze the most important keywords and organizations in the field of biofilm reactors, identifying recent significant papers. Additionally, the paper discusses the opportunities for the future development of biofilm reactors. Through this study, a better understanding of key factors in biofilm reactor research is achieved, providing valuable guidance for future studies and applications in this field.

The detection and analysis of small molecules, typically defined as molecules under 1000 Da, is of growing interest ranging from the development of small molecule drugs and inhibitors to the sensing of toxins and biomarkers. However, due to challenges such as their small size and low mass, many biosensing technologies struggle to have the sensitivity and selectivity for the detection of small molecules. Notably, their small size limits the usage of labeled techniques that can change the properties of small molecule analytes. Furthermore, the capability of real-time detection is highly desired for small molecule biosensors’ application in diagnostics or screening. This review highlights recent advances in label-free real-time biosensing technologies utilizing different types of transducers to meet the growing demand for small molecule detection.

This work compares the multi-element analysis of human hair and nails using inductively coupled plasma mass spectrometry (ICP-MS) with an easy, fast, cheap, non-destructive method using energy dispersive x-ray fluorescence (EDX-RF). The ICP-MS-based method was more sensitive (over 30 elements could be quantified) and costly (requiring more time, sample, and chemicals). The EDX-based method required laboratory and certified reference materials made of hair for instrument calibration. It was less sensitive (16 elements could be quantified: S, Si, Ca, Br, Fe, Cu, Cr, Mg, Si, K, Mn, Ni, Zn, Se, Sr, Pb), but it allowed to replace troublesome grinding with the dissolution of keratin-based material with alkalic agent (tetramethylammonium hydroxide, TMAH) and formation of stable for days pellets. The method is simple, enables automation, and, due to the modification of wells in the autosampler of the EDX system by immersion of home-designed inserts, it requires smaller amounts of biological material and binder (down to 70 mg instead of 500 mg required by commercially available instrument) to perform analysis. It was concluded that the EDX-based method offers complementary selectivity and sensitivity to ICP-MS with the possibility of the reuse of the sample for further analysis.

In this work, a ZIF-67/MWCNTs/Nafion sensor platform was constructed based on the good adsorption capacity of ZIF-67, the electrical conductivity of multiwalled carbon nanotubes (MWCNTs) and the excellent chemical stability of Nafion for the detection of Cu2+ in water. Meanwhile, the modified materials were characterized by scanning electron microscopy (SEM), Transmission electron microscopy (TEM), BET specific surface area test, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Fourier transform infrared spectrometry (FT-IR). Cyclic voltammetry (CV), electrochemical impedance (EIS), and square wave solvation voltammetry (SWSV) electrochemical methods were used to perform applied test studies on ZIF-67/MWCNTs/Nafion/GCE. The results show that ZIF-67/MWCNTs/Nafion/GCE has high sensitivity (57.5 μA/μM) and a low limit of detection (15.0 nM) for the electrochemical detection of Cu2+ ions in an electrochemical sensing system. It has high adsorption selectivity for Cu2+, and the recovery of Cu2+ in real water reached 98.6%-103%. The modified electrode has good repeatability, reproducibility, anti-interference, and stability, which makes this sensing platform can be practically applied to the detection of domestic water.

Patient-derived tumor organoids (PDTOs) are a novel preclinical model of non-small cell lung cancer (NSCLC) for studying tumor biology and precision medicine, which recapitulates tumor morphology and gene expression profile. However, some issues such as low establishment rates, long-term production, and the loss of the immune microenvironment have hindered their widespread practical use. In this study, we investigated the efficacy of a recently introduced free-floating organoid production method to address these issues. The free-floating approach provided PDTO establishment success rate of over 90 % resulting in organoid formation within a short period of one week. These organoids retained the elements of the parental tumor morphology and contained stroma and immune cell populations, as confirmed by flow cytometry analysis. Importantly, we found that the cytokine and growth factor expression profiles of the free-floating organoids correlated with those of the original tumors in 58 % of cases, indicating the preservation of tumor-associated signaling pathways. Obtained organoids exhibited different responses to anticancer chemotherapeutics that might be a result of variable expression of drug resistance-associated genes. Considering the high establishment rate and short time of free-floating organoid production, this technique provides a valuable tool for a more accurate evaluation of therapeutic strategies and cancer biology studies.

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.

Keywords: Cell-free DNA, sepsis, oxidative stress, immunoredox modulation, cecal ligation and puncture, toll-like receptor

This study aims at the sustainable valorization of eggshells (ES) from different countries of origin in cement concrete as a cement replacement for Hong Kong. For this purpose, sixteen different eggs from different regions across the world were selected from the local market. Firstly, the extent of uniformity in the weight and mineral content of sampled eggshells were assessed by a specific gravity test and thermogravimetric analysis (TGA), respectively. It was found that specific gravity varies between 2.02 and 2.39, with an average value of 2.20 ± 0.01, whereas CaCO₃ varies between 94.65% and 97.23%, with an average value of 96.33%. These values were a bit lower than those of extra-pure limestone (LS) because of the organic part and the porous structure of eggshells. Secondly, three different eggshells were selected for cement replacement in cement concrete, both in the uncalcined and calcined states, based on having the highest, medium, and lowest CaCO₃ content, respectively. To get the calcined eggshells, the eggshells were calcined at 800^oC for three hours. It was found that the strength of eggshells varies with CaCO₃, but the variation was acceptable. The calcined eggshells showed comparatively more compressive strength and were close to the LS because of the free CaO and the absence of an organic part. In general, the variation in the basic properties of eggshells from different regions across the world is negligible and suitable to use as a cement replacement with acceptable variation in strength in Hong Kong.

In this study, we propose an efficient field-free line (FFL) generator for mechanically driven FFL-magnetic particle imaging (MPI) applications. The novel FFL generator comprises pairs of Halbach arrays and bar magnets. The proposed design generates high-gradient FFLs with low-mass permanent magnets, realizing fine spatial resolutions in MPI. We investigate the generated magnetic field using simulations and experiments. Our results show that the FFL generator yields a high gradient of 4.76 T/m at a cylindrical field of view of 30 mm diameter and a 70 mm open bore. A spatial resolution of less than 3.5 mm was obtained in the mechanically driven FFL-MPI.

Metal halide perovskites have shown excellent optoelectronic properties, including high photoluminescence quantum yield, tunable emission wavelength, narrow full-width at half-maximum and low-cost solution-processed fabrication, which make it exhibit great potential as the emission layer materials of light emitting diodes. With the joint efforts of researchers from different disciplines, there has been a significant progress in the improvement of external quantum efficiency (EQE) and stability of perovskite light emitting diodes (PeLEDs) in recent few years, especially in green PeLEDs with EQE over 30%. In this review, we firstly introduce the basic device structure of PeLEDs, as well as the factors influencing EQE and stability of PeLEDs. Secondly, the development of lead-based and lead-free PeLEDs are summarized systematically. Thirdly, challenges of PeLEDs are discussed in detail, including low EQE of blue PeLEDs, poor device stability and EQE roll-off. Finally, some suggestions and perspectives of the future research directions for PeLEDs are proposed.

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.

Metal-Organic Frameworks (MOFs) have been observed to exclusively eliminate dyes confined within their respective pores. In this investigation, the synthesis of a breathable MOF structure, MIL-88B(Fe), was pursued with the objective of circumventing restrictions on pore size to en-hance its adsorption capabilities. The synthesis of MIL-88B(Fe) was carried out via the assisted solvothermal method at 373 K using inexpensive yet environmentally benign FeCl3.6H2O, 1,4-benzenedicarboxylic acid and DMF as metal precursor, as linker and solvent, respectively. Furthermore, MOF was subjected to extensive analytical characterization using XRD, FT-IR spectroscopy, N2 gas sorption, TGA, and SEM. The experimental data showed that the utilization of MIL-88B(Fe) with a dose level of 5 mg for 180 mins at pH of 9 led to the highest levels of ad-sorption for both dyes with 162.82 mg g-1 for Methylene Blue (MB) and 144.65 mg g-1 for Rho-damine B (RhB), as a result of contrast molecular size between each dye. The Langmuir and Freundlich models demonstrate a correlation with isotherms, while the thermodynamic analysis demonstrated that MIL-88B(Fe) exhibits distinct endothermic and breathable properties. The ef-ficacy of MIL-88B(Fe) adsorbent for MB and RhB in aqueous solutions indicated exceptional performance, stability, and noteworthy reusability performance.

The indole nucleus is an important element of many natural and synthetic molecules with significant biological activity. Nonetheless, the co-presence of transitional metals in organic scaffold may represent an important factor in the development of effective medicinal agents. This review covers some of the relevant and recent achievements in the biological, chemical and pharmacological activity of important indole-based metal complexes in the area of drug discovery.

Background: The proven efficacy of mTOR inhibitors (mTORI), tyrosine kinase inhibitors (TKI) or immune checkpoint inhibitors (ICI) therapies in metastatic renal cell carcinoma (RCC), suggested that these agents should be investigated as adjuvant therapy with the aim of eliminating any residual undetectable microscopic disease after curative resection. Our study aimed to compare the efficacy of these treatments through the application of an innovative method that reconstructs individual patient data. Methods: Nine phase III studies describing different treatment options for adjuvant RCC were selected. Individual patient data were reconstructed from Kaplan–Meier (KM) curves through the “IPDfromKM method”. Disease-free survival (DFS) were compared among combination treatments and control arm (placebo). Results were summarized as multi-treatment KM curves. Standard statistical testing was used, including hazard ratio and likelihood ratio tests for heterogeneity. Results: In the overall population, this study showed that two ICIs (pembrolizumab and nivolumab plus ipilimumab) and one TKI (sunitinib) showed superiority over placebo, whereas both TKI and mTORI did not. As we assessed DFS as the primary endpoint for the adjuvant comparison, the overall survival benefit remains unknown.. Conclusion: This novel approach to investigating survival has allowed us to conduct all of the indirect head-to-head comparisons between these agents in a context where no "real" comparative trials have been conducted.

Gastric outlet obstruction (GOO) poses a common and challenging clinical scenario, characterized by mechanical blockage in the pylorus, distal stomach, or duodenum, resulting in symptoms such as nausea, vomiting, abdominal pain, and early satiety. Its diverse etiology encompasses both benign and malignant disorders. The spectrum of current treatment modalities extends from conservative approaches to more invasive interventions, incorporating procedures like surgical gastroenterostomy (SGE), self-expandable metallic stents (SEMS) placement, and the advanced technique of endoscopic ultrasound-guided gastroenterostomy (EUS-GE). While surgery is favored for longer life expectancy, stents are preferred in malignant gastric outlet stenosis. The novel EUS-GE technique, employing a lumen-apposing self-expandable metal stent (LAMS), combines the immediate efficacy of stents with the enduring benefits of gastroenterostomy. Despite its promising outcomes, EUS-GE is a technically demanding procedure requiring specialized expertise and facilities.

Modification the biodegradable matrix was carried by graft-copolymerization polylactide with methacrylic acid of various concentrations. Ultraviolet irradiation with different exposure times to the samples was chosen as the initiator of copolymerization. In the experiment the effect of ultraviolet light on polylactide and graft copolymerization was investigated: the resulting samples were studied by viscosimetry, gravimetry, FTIR, static cation- exchange capacity analysis . The conditions for obtaining grafted copolymers and the dependence of the characteristics on the reaction conditions are established.

Resveratrol is currently considered an option for chemoprevention and treatment of oral cancer, but the instability and unfavorable pharmacokinetics hinder its use in clinical practice. The present study deals with the preparation of resveratrol liposomes by a method that preserves stability and provides payload high enough for chemoprevention and/or treatment of oral cancer. Different temperatures, RSV concentrations and molar fractions, as well as the presence or absence of vitamin C in the hydration media were assayed. Liposome hydrodynamic diameter, polydispersity and zeta potential were evaluated by dynamic light scattering. In vitro biocompatibility, antioxidant activity and permeability were evaluated using TR146 cells and PermeaPad® membranes. Liposomes were included in hydrogels and films, and their suitability for buccal application was evaluated. According to the results, a temperature of 37ºC was optima to efficiently produce the resveratrol liposomes. Vitamin C was found to influence the liposome size, while resveratrol concentration significantly influenced the entrapment efficiency. High cell biocompatibility and potent intracellular antioxidant activity were observed and the inclusion of vitamin C reinforced the antioxidant effects. High permeation across PermeaPad® membranes and efficient uptake by TR146 cells was proved for resveratrol loaded liposomes. Liposomal hydrogels and films appropriated for buccal application were obtained and the payload of the formulations was high enough to produce mucosa concentrations above resveratrol IC50 values reported for cancer cells.

This study conducts a comprehensive analysis of the presence of heavy metals, including zinc (Zn), lead (Pb), copper (Cu), chromium (Cr), and arsenic (As), in the dust found inside educational buildings and the top layer of soil in different areas of Vilnius. The study focuses on the analysis of topsoil samples gathered between 2011 and 2023, with a specific emphasis on dust samples obtained from 24 schools in 2022. The research reveals significant variations in the concentrations of heavy metals, providing a clear understanding of the complex relationship between sources of urban pollution, environmental processes, and the correlation between soil and dust contamination by heavy metals. Indoor dust in schools shows unique contamination patterns in contrast to topsoil, suggesting distinctive sources of indoor pollution, while there are some general similarities. This finding emphasizes similarities and distinctions between soil and dust in educational environments. The study utilizes advanced statistical methods such as Pearson correlation, Principal Component Analysis (PCA), and hierarchical clustering to examine the distribution and characteristics of these metals. This study distinguishes itself by examining indoor dust in educational facilities and topsoil in Vilnius, providing crucial insights into the relationship between these two environmental matrices.

We discuss how the interaction of electrons with an overdamped optical phonon can give rise to a strange-metal behavior over extended temperature and frequency ranges. Although the mode has a finite frequency, an increasing damping shifts spectral weight to progressively lower energies so that, despite the ultimate Fermi liquid character of the system at the lowest temperatures and frequencies, the transport and optical properties of the electron system mimic a marginal Fermi liquid behavior. Within this shrinking Fermi liquid scenario, we extensively investigate the electron self-energy in all frequency and temperature ranges, emphasizing similarities and differences with respect to the marginal Fermi liquid scenario.

To address the challenges associated with the difficult electromagnetic (EM) scattering computations of anisotropic dielectric-coated metallic composite targets, we proposed an efficient hybrid algorithm for simulating the EM scattering of complex targets with anisotropic dielectric coatings. This method, based on Impedance Boundary Condition (IBC), utilizes surface impedance vectors to describe the EM properties of the dielectric. It fully leverages the respective advantages of the low-frequency Method of Moments (MoM) and the high-frequency Physical Optics (PO) to achieve high-precision and rapid EM simulation of anisotropic dielectric-coated metallic composite targets. Employing boundary conditions and equivalent principles, we equivalently transform the EM scattering problem of targets with thin dielectric coatings into the radiation problem of equivalent EM current on impedance surfaces. This enables the high-precision and rapid calculation of Radar Cross Sections (RCS) for complex targets with anisotropic dielectric coatings. Using examples such as a square plate structure, a simplified aircraft, and a complex satellite model, the simulation results exhibit a high degree of agreement with full-wave numerical solutions and demonstrate a significant advantage in computational resources. This research convincingly demonstrates the accuracy and effectiveness of the proposed method.

The genetic engineering of plants often relies on the use of antibiotic or herbicide resistance genes for initial selection of primary transgenic events. Nevertheless, the commercial release of genetically modified crops containing any marker gene encounters several challenges stemming from the lack of consumer acceptance. Development of strategies enabled the generation of marker-free transgenic plants is a possible alternative to deal with public concerns over the safety of biotech crops. Leveraging the high in vitro regeneration and transformation capabilities of potato, this study examined the factors associated with the development of transgenic plants without presence of selective substances in medium. To compare the antibiotic-assisted with the antibiotic-free transformation, nodal explants from five highly regenerative potato cultivars were inoculated with the Agrobacterium strain AGL0 carrying the pBIN-mGFP5-ER (35SGFP/nosNPTII) plasmid. The efficiency of transient expression and the formation of chimeric and completely transgenic shoots were assessed through vital GFP observations. Under non selective conditions, the regeneration efficiency of stable non-chimeric transgenic shoots varied from 0.9 (‘Chicago’) to 2.7% (#12-36-42). In order to streamline transformation protocol, a specific timeline for collecting transgenic plantlets was established for each analyzed cultivar. This timeline strategy was implemented to generate transgenic potato plants, which demonstrated the suppression of homologous SteIF4Es family genes as a result of the successful introduction of the marker-free hpRNAi construct.

The strength of laser joined metal and plastic hybrids is based purely on adhesion. Unpolar plastics like polypropylene depend solely on the mechanical adhesion while polar plastics like polyamide 6.6 develop covalent bonds with the metal. In this research the influence of different surface metallizations on the lap shear strength of laser joined hybrids was investigated. Sandblasted AISI 304 was used as base metal and reference. Aluminum and titanium coatings were deposited by the means of Arc-PVD. Polypropylene and polyamide 6.6 were utilized as polar und unpolar plastics. The lap shear strength of all hybrids with polyamide 6.6 was higher than the polypropylene samples. For all investigated variations of the laser power, scanning speed and the cohesive and adhesive failure modes, the samples joined with the sandblasted AISI 304 showed the highest lap shear strength. The reduction in lap shear strength for the coated samples was due to the increased difference in thermal conductivity between the plastics and the coating materials. This lead to increased warping and residual stresses. It can be concluded that the thermal properties of the metallization in laser joined metal and plastic hybrids has a high impact on the lap shear strength.

Dimers and oligomers of alkenes represent a category of compounds that are in great demand for diverse industrial sectors. Among the developing synthetic methods, the catalysis of alkene dimerization and oligomerization using transition metal salts and complexes is of undoubted interest for practical application. This approach demonstrates substantial potential, offering not only elevated reaction rates but also precise control over the chemo-, regio-, and stereoselectivity of the reactions. In this review, we discuss the data on catalytic systems for alkene dimerization and oligomerization. Our focus lies in the analysis of how the activity and chemoselectivity of these catalytic systems are influenced by various factors, such as the nature of the transition metal, the ligand environment, the activator, and substrate structure. Notably, the review particularly discusses the reaction mechanisms, encompassing metal complex activation, structural and dynamic features, and the reactivity of hydride intermediates, which serve as potential catalytically active centers in alkene dimerization and oligomerization.

We report a simple and high-performance flexible strain sensor based on liquid metal nanoparticles (LMNPs) on polyimide substrate by laser induced deposition. The LMNPs were prepared by ultrasonic method, and then the femtosecond laser direct writing technology was used to induce the assembly and deposition of the LMNPs to form liquid metal microwires. Laser local sintering enhances the connection between particles, and a wearable strain sensor was fabricated with the high sensitivity as high as 76.18, the good linearity (a correlation coefficient of 0.999) in a wide sensing rage, the fast response/recovery time of 159 ms/120 ms. Attributed to these extraordinary strain sensing performances, the sensor can sense various dynamic strains in real time, monitor both subtle physiological activities and large human motions. It can be adhered to human skin, and well reflect the change of facial expression and realize real-time monitoring of facial expression. And the vocal cord vibration can be detected for speech recognition while the sensor attached to the outside of the throat.

Transportation is the primary consumer of oil, accounting for a significant portion of global energy consumption (34%) and CO2 emissions (40%). Electrifying road transportation is crucial to mitigate the effects of global warming. The abundant potential of renewable energy sources like solar and wind is hindered by their intermittent nature and incongruity with peak energy demands. This calls for the development of sophisticated energy storage solutions. Metal-air batteries (MABs), emerging as viable alternatives to lithium-ion batteries (LIBs), have attracted considerable attention due to their promising applications in the transportation sector. Despite substantial progress in MAB development over the past two decades, overcoming critical challenges such as electrolyte decomposition, carbon cathode degradation, anodic dendrite growth, and air impurities remains essential for their commercial viability. This mini-review provides a comprehensive overview of MAB fundamentals and the challenges associated with their development. The insights presented in this review serve to illuminate the current landscape and future prospects of MABs in the transportation sector.

The CMT (Cold Metal Transfer) arc welding process is a convenient instrument for the assembly of thin sheets [1], [2]. More particularly, it permits the decrease of the amount of heat transferred to the parts to-be assembled, thus reducing their subsequent deformations. The present work aims at simulating the CMT welding of thin stainless-steel sheets in order to develop an approach that allows the prediction of temperature fields, as well as final deformations induced by the welding process. For that purpose, instrumented tests and numerical simulations were set aiming at comparing the experiments with simulations. Butt-welding of stainless-steel sheets was considered, with a thickness ranging from 1 to 1.2 mm. The weld seam samples were observed in order to set an equivalent heat source for each configuration. Moreover, the electric current and voltage were surveyed, and temperature measurements were performed using K-type thermocouples. In addition, displacement measurements were obtained using the DIC (Digital Image Correlation) technique. Thermomechanical simulations were then carried out using an equivalent heat source approach, considering the phase changes of elements, i.e. the transitions from solid to liquid and from liquid to solid. These simulations also consider the actual geometry of seams induced by addition of a filler material.

This paper introduces new improvements to the modified version of the BIRECT (BI secting RECTangles) algorithm referred to as BIRECTv. We explore various approaches, by first including a grouping strategy for hyper-rectangles having almost the same sizes by categorizing them into different classes. Therefore constraining them not to exceed a certain pre-defined threshold (a small positive value to define the tolerance level). This approach allows for more efficient computation and can be particularly useful when dealing with a large number of hyper-rectangles with varying sizes. To avoid over-sampling, and preventing redundant or excessive sampling, at some shared vertices in descendant subregions, a particular vertex database is used to limit the number of samples taken within each subregion to two. The experimental investigation shows that these improvements have a positive impact on the performance of the BIRECTv(imp.) algorithm and the proposal is a promising global optimization algorithm compared to the original BIRECTv algorithm and its variants. Additionally, the BIRECTv(imp.) algorithm showed particular efficacy in solving high-dimensional problems.

In the context of circular economy that recommends the most efficient use of waste, algae wastes have a huge potential for valorisation. In this study, algae wastes obtained after alkaline extraction of active compounds from two types of marine algae (green algae – Ulva sp. and red algae – Callithamnion sp.), were used as biosorbents to remove metal ions from aqueous effluents. Their efficiency in the biosorption processes was tested for Zn(II), Cu(II) and Co(II) ions, considered technologically valuable metal ions. The batch mono-component experiments performed under optimal conditions (pH = 5.0; 4.0 g biosorbent/L; 22 ± 1C), showed that more than 75 % of the metal ions are removed when their initial concentration is less than 1.25 mmol/L. The very good fit of the experimental data with the pseudo-second order kinetic model and Langmuir isotherm model, and the high values obtained for the maximum biosorption capacity (qmax: Cu(II) (0.52 mmol/g) > Zn(II) (0.41 mmol/g) > Co(II) (0.39 mmol/g) for G-AWB, and qmax: Cu(II) (1.78 mmol/g) > Zn(II) (1.72 mmol/g) > Co(II) (1.66 mmol/g) for R-AWB) highlights the potential use of these biosorbents to remove such technologically valuable metal ions from industrial wastewater. This possibility was tested using industrial wastewater samples obtained from the metal coating industry. Quantitative removal (> 91 %) of Zn(II), Cu(II) and Co(II) ions was obtained when their initial concentration was adjusted to 50 mg/L. Also, the rapid and efficient desorption of these metal ions from loaded-biosorbents, by simple treatment with small volumes of HNO3 (10-1 mol/L), further emphasizes the possibility of their recovery and reuse in the technological circuit. The results included in this study indicate that algae wastes have the potential to be used in industrial effluents decontamination processes and opens new perspectives for the implementation of circular economy principles.

Recently, considerable work has been directed at development of a ultra-compact X-ray free-electron laser based on emerging techniques in high field cryogenic acceleration, with attendant dramatic improvements in electron beam brightness, and state-of-the-art concepts in beam dynamics, magnetic undulators, and X-ray optics. A full conceptual design of a 1 nm XFEL with a length and cost over an order of magnitude below current XFELs has resulted from this effort. This instrument has been developed with an emphasis on permitting exploratory scientific research in a wide variety of fields in a university setting. Concurrently, compact FELs are being urgently developed for use as an instrument to enable next generation chip manufacturing through use as a high flux, few-nm lithography source. This new role suggests consideration of XFELs to addressed urgently emerging demands in this sector, as identified by recent national need studies, for new radiation sources aimed at chip manufacturing: a coherent hard X-ray source which enables frontier metrology methods. Indeed, it has been shown that one may use coherent X-rays to perform 10 nm-class resolution surveys of macroscopic, cm-scale structures such as chips, using ptychographic laminography. As the XFEL is a very promising candidate for realizing such methods, we present here an analysis of the issues and likely solutions associated with extending the UCXFEL to harder X-rays (above 7 keV), much higher fluxes and levels of coherence, and methods of applying such a source for ptychographic laminography to micro-electronic device measurements. We discuss the development path to move the concept to rapid realization of a transformative FEL-based application, outlining FEL and metrology system challenges.

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.

Celiac disease is an autoimmune disease triggered by oral ingestion of gluten, with certain gluten residues resistant to digestive tract enzymes. Within the duodenum, the remaining peptides incite immunogenic responses, including the generation of autoantibodies and inflammation, leading to irreversible damage. Our previous exploration unveiled a glutenase called Bga1903 derived from the Gram-negative bacterium Burkholderia gladioli. The cleavage pattern of Bga1903 indicated its moderate ability to mitigate the toxicity of pro-immunogenic peptides. The crystal structure of Bga1903, along with the identification of subsites within its active site, was determined. To improve its substrate specificity toward prevalent motifs like QPQ within gluten peptides, the active site of Bga1903 underwent site-directed mutagenesis according to structural insights and enzymatic kinetics. Among the double-site mutants, E380Q/S387L exhibits an approximately 38-fold increase in its specificity constant toward the QPQ sequence, favoring glutamines at the P1 and P3 positions compared to the wild type. Not only does the heightened specificity of E380Q/S387L improve the hydrolytic activity against pro-immunogenic peptides, but also holds this version of the enzyme as a promising candidate as an oral therapy enzyme for celiac disease.

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).

The results of a study of the processes of formation of macro- and micro-inhomogeneity of ingots and rolled sheets are presented. To study the nature and sources of surface defects in rolled sheets, a comparative method of structural-concentration analysis of metal at the end-to-end metallurgical process of ingot - slab - sheet metal has been developed, based on the metallographic method of studying the structure and qualitative analysis of non-metallic inclusions. The research results showed that the quality of the surface of rolled sheets is determined mainly by the physical heterogeneity of the crust zone of the ingots, and the internal defects of thin rolled sheets largely depend on the contamination of the metal with non-metallic inclusions and off-axis segregation. A mechanism for transforming defects in the casting cortical zone into surface and internal defects in rolled sheets is proposed.

The paper presents the numerical and experimental results of research aimed at determining the influence of hardness in the range of 50-90 Shore A of layered tools made of elastomeric materials on the possibility of forming Inconel 625 nickel-based alloy sheets. A stamping die made of 90MnCrV8 steel (hardness 60HRC) was designed for forming embosses in drawpieces, ensuring various stress states on the cross-section of the formed element. The principle of operating the stamping die was based on the Guerin method. Finite element-based numerical modelling of the forming process for various configurations of polyurethane inserts was also carried out. The drawpieces obtained by sheet forming were subjected to geometry tests using optical 3D scanning. The results confirm that in the case of forming difficult-to-deform Inconel 625 Ni-based alloy sheets, the hardness of the polyurethane inserts significantly affects the geometric quality of the obtained drawpieces. The assumptions made in numerical simulations were verified in experimental studies. Based on the test results, it was concluded that the selection of polyurethane hardness should be determined by the shape of the formed element. Significant non-uniform sheet metal deformation was also found, which may pose a problem in the process of designing forming tools and technology of plastic forming of Inconel 625 Ni-based alloy sheets.

The growing adoption of distributed energy production technologies, and the potential of energy underutilization when it is produced by non-connected groups, has raised interest in ‘sharing economy’ concepts in the electricity sector. We suggest that mechanisms, such as peer-to-peer (P2P) energy trading, will allow users to exchange their surplus energy for mutual benefits, stimulate the adoption of renewable energy, encourage communities to ‘democratically’ control their own energy supplies for local development, and improved energy efficiency, and create many other benefits This approach is receiving increasing attention across the world, particularly in Germany, the Netherlands and Australia. Nevertheless, the actual development and implementation of these platforms is slow and mostly limited to trial activities. This study investigates the challenges and barriers facing P2P energy trading developments based on previous academic and industry studies. We provide a comprehensive multidimensional barrier analysis through a PESTLE approach to assess the barriers from a variety of perspectives, including the political (P), economic (E), social (S), technological (T), legal (L), and environmental (E) aspects. This approach clarifies the many intersecting problem fields of P2P trading in renewable energy, and the paper identifies a list of such barriers, and discusses the prospects for addressing these issues. We also elaborate on the importance of incentive-based P2P market design.

Studies involving vortex in hybrid superconducting devices and their interaction with different components inside the sample are an important issue to reach higher values of their critical parameters in superconducting materials. The vortex distribution on each side of sample with different fundamental parameters, such as temperature T, penetration depth λ, coherence length ξ, electron mass m and the order parameter Ψ, may help to improve the superconducting properties. Thus, in this work, we used the modified Ginzburg-Landau theory to investigate hybrid superconductor (HS), but also to provide a highly tunable and adjustable theoretical tool to theoretically explain the experimental results involving HS, in order to study the vortex behaviour in superconductors of mesoscopic dimensions with extremely differences among their fundamentals parameters. Therefore, we evaluated the influence of HS on vortex configuration and their effects in the field-dependent magnetization. The results show that the during the increment of applied magnetic field H the diamagnetic response of HS, Meissner effect, include additional jumps of magnetization while diamagnetism continues its increase in the sample. In addition, the differences among parameters, create an interface between both components, two different magnitudes of supercurrent and vortex sizes producing a lower degradation of local superconductivity, which increase the upper critical field. On the other hand, this type HS with differences of parameters on both sides can be used to control the vortex movement in the selected superconducting region sample with more accuracy.

Metals are particularly sensitive to some pollutant gases. Many museum showcases and store rooms present atmospheres that can corrode cultural heritage artefacts containing metals. Whilst numerous strategies have been reported to mitigate such situations, avoiding them is preferable. Several approaches to testing materials used in construction, fitting out or dressing are used. The relative merits and drawbacks will be discussed. Several parameters of the most widely used, the accelerated corrosion ‘Oddy’ test have been investigated. The influence of abrasive on subsequent corrosion of lead and copper coupons have been assessed. Quantification methods for tested coupons are reviewed. The influence of test duration and temperature were assessed through comparison with real life, long term experience of materials behaviour. Direct contact tests with the material tested touching the test material has been investigated. Several materials present in artefacts are known to potentially cause corrosion when enclosed with metals in other artefacts. A number of situations have been investigated with pollution and RH and some corrosion rate measurements. Ways to isolate artefacts or mitigate are explored and a decision support model has been developed.

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.

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 study investigates novel ferrocene-based electrochemical sensors for metal cation detection through the design, synthesis and characterisation of ferrocene derivatives. Specifically, the re-search determines the redox potentials of ferrocene versus decamethylferrocene to provide in-sight into the redox potential variations between them. The investigation also examines how electrochemical oxidation of the ferrocene moiety can modulate host affinity for transition metals cations via effects such as electrostatic interactions and changes to coordination chemistry. Metal ion coordination to receptors containing functional groups like imine and quinoline is explored to elucidate selectivity mechanisms. These findings advance the fundamental understanding of ferrocene electrochemistry and host-guest interactions, supporting the development of improved cation sensors with optimised recognition properties, sensitivity, and selectivity. Overall, the work lays the necessary groundwork for applications in analytical chemistry and sensor technologies through customised ferrocene-derived materials.

Background: Malnutrition was associated with worse survival outcomes, impaired quality of life, and deteriorated performance status across various cancer types. We aimed to identify risk factors for malnutrition in patients with epithelial ovarian(EOC) and impact on survival. Methods: In our prospective study, we included the patients with primary and recurrent EOC, tubal or peritoneal cancer conducted. We assessed serum laboratory parameters, body mass index, nutritional risk index, nutritional risk screening score(NRS-2002), and bio-electrical impedance analysis. Results: We recruited a total of 152. Patients >65 years-old, with ascites of >500 ml, or with platinum-resistant EOC showed statistically significant increased risk of malnutrition when evaluated by NRS-2002(p-values = 0.014, 0.001, and 0.007, respectively). An NRS-2002<3 was an independent predictive factor for complete tumor resectability (p=0.009). The patients with NRS-2002≥3 had a median overall survival(OS) of seven months (95% CI=0-24 months), as compared to the patients with NRS-2002<3 where median OS was 46 months(p=0,001). Phase angle(PhAα)≤ 4.5 was the strongest predictor of OS. Conclusion: Malnutrition is an independent predictor of incomplete cytoreduction in study population. It is an independent prognostic factor for poor OS. Preoperative nutritional assessment is an effective tool in identification of high-risk groups within EOC characterized by poor clinical outcome.

Background: This study retrospective evaluates patients with stage IV melanoma treated with Nivolumab and Ipilimumab combination therapy from two regional oncology centers from Romania between the years of 2019 up to the end of 2022. Methods: The data were analyzed in SAS for Windows, V9.4. The survival curves were estimated using the Kaplan-Meier method, and survival distributions were compared with log-rank test. The effects of the main clinical and pathological variables on OS and PFS were investigated with Cox regression. Results: Kaplan-Meier curve of OS in all evaluable patients enrolled in the study resulted in a median OS of 346 days (95% CI: 150-NA) and a median PFS of 211 days (95% CI: 113-430). 45.3% of the patients experienced adverse events during the Nivolumab + Ipilimumab treatment with some of them having multiple organ systems involved. Discussion: The OS values were lower than that reported in approval clinical trials, but the results show a marked improvement when comparing to results obtained by chemotherapy regimens previously used in these scenarios. Conclusion: This study provides real-world insights into the survival data and safety profiles of combination therapy with anti-PD-1 antibodies and anti-CTLA-4 antibodies.

The fusion of surface-modified steel with tungsten carbide (WC) and NiCrBSi powder through laser metal deposition has emerged as a formidable strategy for fortifying components against wear and corrosion in extreme operating environments. Meticulous selection of WC content, innovative pre-alloying techniques, and precise control of laser metal deposition profoundly influence the mechanical properties and microstructural evolution of WC-NiCrBSi coatings applied to surface-enriched commercial alloy steel (805M2, 832M13, and 827M40). These tailored coatings exhibit exceptional resilience, ideal for harsh industrial settings in Oil and gas drilling, petrochemical, and Mining sectors. Advanced materials testing techniques, including scanning electron microscopy, light optical microscopies, and microhardness testing, unveil the innate hardness attributes, with findings highlighting the unassailable fortitude of the Mixed matrix layer's side face. The amalgamation of these testing methodologies with laser metal deposition promises an unparalleled path to extend the operational lifespan of critical components in challenging working conditions. The research horizon for WC-NiCrBSi coatings remains broad, with the potential to enhance durability, operational efficiency, and cost-effectiveness across diverse applications.

Band structure calculations using the spin-polarized relativistic Korringa-Kohn-Rostoker (SPRKKR) band structure method have been performed to determine the intrinsic magnetic properties (magnetic moments, magneto-crystalline anisotropy -MAE and Curie temperatures) of the Fe5-x-yCoxMySiB2 (M = Re, W) alloys. The general gradient approximation for ex-change-correlation potential and the atomic sphere approximation (GGA ASA) have been em-ployed. Previous studies showed that the Co doping is turning the in-plane into axial anisotropy for a certain doping range, whilst the 5d doping enables a strong spin-orbit coupling of Fe-3d and M-5d states which is needed to enhance the MAE. The theoretical calculations aim to find the dependence of the anisotropy constant K1 for combined Co and M doping, building a two-dimensional (2D) map of K1 for 0 ≤ x ≤ 2 and 0 ≤ y ≤ 1. Similar theoretical 2D maps for magnetization and Curie temperature vs. Co and M content (M = W and Re) have been built, allowing to select alloy compositions with enhanced values of uniaxial anisotropy, magnetization and Curie temperature. Magnetic properties of Fe4.1W0.9SiB2 alloy that meets the selection criteria for axial anisotropy K1 > 0.2 meV/f.u., Curie temperature Tc > 800 K determined by mean field approach and magnetization µ0Ms > 1 T are discussed.

Cancer remains as a worldwide cause of death. Investigational research efforts have included the administration of tumors-derived extracts to healthy animals. Having previously demonstrated that administration of non-transmissible, human cancers-derived homogenates induced malignant tumors in mice; we examined here the consequences of administering 50 or 100 µg of protein of crude homogenates from samples of mammary carcinoma, pancreatic adenocarcinoma, and melanoma. The protocol conceived six inoculations per week during three months. Concurrent control group received homogenates of healthy donor skin cosmetic surgery fragments. Mammary carcinoma homogenate administration did not provoke animals’ deterioration or mortality. Multiple foci of lung adenocarcinomas with broad expression of malignity histomarkers, coexisting with small cell-like carcinomas were found. Disseminated cells, positive to classic epithelial markers were detected in lymphoid nodes. Pancreas tumor and melanoma homogenates administrations severely deteriorated animals’ health. Pancreas tumor induced lung poorly-differentiated adenocarcinomas, as a remarkable pancreatic islets hyperplasia. Melanoma affected lungs with atypical adenomatous hyperplasia and solid pseudopapillary adenocarcinoma. Giant atypical hepatocytes with variegated nuclei were also observed. Kidney parenchyma exhibited dispersed foci of neoplastic cells within a desmoplastic matrix. A noticeable nuclear overlapping with hyperchromatic nuclei, mitotic figures, and prominent nuclear atypia was identified in epidermal cells. None of these changes were ever detected in any mouse of the control groups. This study confirms and extends our hypothesis that tumor homogenates contain and may act as a vector for “malignancy drivers”, which ultimately implement a carcinogenesis process in otherwise healthy mice.

.Celiac disease (CeD) is a chronic, autoimmune disorder triggered by the ingestion of gluten, affecting around 1% of the global population. It is a multifactorial disease involving both genetics and environ-mental factors. Nowadays, the only available treatment for CeD is a life-long gluten-free diet (GFD), which can cause a significant burden for patients, since symptoms and mucosal injury can persist de-spite apparent compliance with a GFD. That could also lead to psychological consequences and affect the quality of life of these patients. Thankfully, recent advances in understanding the pathogenesis of CeD and the availability of various targets have made it feasible to explore pharmaceutical treatments specific to CeD. Recently, the FDA has highlighted the unmet needs of adult patients on GFD who expe-rience ongoing symptoms attributed to CeD and also show persistent duodenal villous atrophy. This re-view will outline the limitations of a GFD, describe the targets of potential novel treatment of CeD and provide an overview of the primary clinical trials involving oral and injectable agents for a non-dietary treatment of CeD.

Accurate pathogenic detection in wastewater is critical for safeguarding public health and the environment. However, the presence of free nucleic acids in wastewater samples poses significant challenges to molecular detection accuracy. This comprehensive review explores the current status and future potential of pretreatment methods to remove free nucleic acids from wastewater samples. The study contributes a comprehensive analysis of the mechanisms, strengths, and limitations of various pretreatment approaches, including physical, chemical, and enzymatic processes. The effect of various factors on the removal efficiency of these pretreatment methods is also discussed. This review enhances our comprehension of pretreatment techniques and their vital role in achieving precise pathogenic detection in complex wastewater matrices. Furthermore, it outlines future perspectives and developments for improving the speed and effectiveness of pathogenic detection, contributing significantly to disease surveillance, early warning systems, and environmental protection.

Serologic measures of tissue transglutaminase (tTG) immunoglobulin A (IgA) and deamidated gliadin peptide (DGP) IgA and immunoglobulin G (IgG) are hallmark tests utilized when diagnosing individuals for celiac disease (CeD) and for monitoring adherence to a gluten-free diet (GFD), currently the only available treatment for CeD. We address two issues in this study: (i) the relapse to seropositivity for CeD patients who resume a gluten containing diet and (ii) the correlation between two different tTG-IgA assays near the upper limit of normal (ULN) designated thresholds. Regarding the first issue, often a suspected CeD individual is put back on a gluten diet to return to their serologic levels. However, we show it requires a substantial amount of gluten for serology to return to a positive level. For example, in one study of 22 patients treated with placebo and taking 84 g of gluten over 6 weeks, only 2 converted from seronegative to seroposi-tive for tTG-IgA. Regarding the second topic, we compare the relationship for different serologic assays, namely tTG-IgA AB (recombinant, ULN=4 Units/mL) vs. tTG-IgA (non-recombinant, ULN=20 Units). There is a strong correlation by both measurements as evidenced by a Pearson coefficient of R = 0.8584. However, we observed that the cross-correlation in terms of sensitivity and specificity improved substantially by using an ULN value of 3 instead of 4 for the tTG-IgA AB (recombinant) assay. This result suggests that assay thresholds used for initial diagnosis in patients who have not yet started a GFD may need to be adjusted for monitoring and in the setting of a diagnostic gluten challenge.

Modern lifestyle has increased our utilization of pollutants such as heavy metals, aromatic compounds, and contaminants of emerging concern including pharmaceutical and personal products and other materials that may have an important environmental impact. Especially, the ultimate results of intense use of highly stable materials, such as heavy metals and chemical restudies are that they turn into waste materials which, when discharged, accumulate in the environment water bodies. In this context, the present review presents application of metal-organic frameworks (MOFs) in electrochemiluminescent (ECL) sensing for water pollutant detection. MOF composites applied as innovative luminophore or luminophore carriers, materials for electrode modification and enhancement of co-reaction in ECL sensors have enabled sensitive monitoring of some most common contaminants of emerging concern such as heavy metals, volatile organic compounds, pharmaceuticals, industrial chemicals and cyanotoxins. Moreover, we provide future trends and prospects associated with ECL MOF-composites for environmental sensing.

Protein tyrosine phosphatases (PTPs) of the polymerase and histidinol phosphatases (PHP) superfamily with characteristic phosphatase activity dependent on divalent metal ions are found in many gram-positive bacteria. Although members of this family are co-purified with metal ions, they still require the exogenous supply of metal ions for full activation. However, the specific roles these metal ions play during catalysis are yet to be well understood. Here, we report the metal ion requirement for phosphatase activities of S. aureus Cap8C and L. rhamnosus Wzb. AlphaFold-predicted structures of the two PTPs suggest that they are members of the PHP family. Like other PHP phosphatases, the two enzymes have catalytic preference for Mn2+, Co2+, and Ni2+ ions. Cap8C and Wzb show an unusual thermophilic property with optimum activities over 75oC. Pre-incubation experiments show that the two enzymes are not inherently thermostable suggesting that certain catalytic step(s) in the reaction mechanism has a high activation energy. Consistent with this model, the activity-temperature profiles of the two enzymes are dependent on the divalent metal ion activating the enzyme.

The emergence of antimicrobial resistance remains one of the greatest public health concerns. Biofilm formation has been postulated as a mechanism of microbial pathogens to resist antimicrobial agents. Lactic Acid Bacteria (LAB) and their metabolites have been proposed to combat bacterial biofilms, due to their antimicrobial activity. In this vein, the aim of the present study was to investigate the biofilm removal potential of cell-free supernatant (CFS) of five wild-type Lacticaseibacillus rhamnosus LAB strains, isolated from Greek natural products, in comparison to the commercial available L. rhamnosus GG strain, formed by common foodborne pathogens (Salmonella Enteritidis, Salmonella Typhimurium, Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus). Biofilm removal activity of LAB was assessed on two-days mature biofilm using a microtiter plate-based procedure. Both non-neutralized and neutralized CFSs removed biofilms in a concentration-dependent manner. Biofilm removal activity of the non-neutralized CFSs was significantly higher compared to the neutralized CFSs, as expected, ranging 40 – 90% and 10 – 78%, respectively. Biofilm removal efficiency of L. rhamnosus OLXAL-3 was signifanctly higher among the wild-type L. rhamnosus strains tested (20 – 100% v/v). In conclusion, our results suggested the great potential of application of wild-type Lacticaseibacillus rhamnosus strains CFSs as effective natural agents against pathogenic bacterial biofilms.

The increading emission of carbon dioxide to the atmosphere has urged the scientific community to investigate alternatives to alleviate such emissions being the principal contributor to the greenhouse gas effect. One major alternative is carbon capture and utilisation (CCU) towards the production of value-added chemicals using diverse technologies. This work aims at the study of the catalytic potential of different cobalt-derived nanoparticels for methanol syntheis from carbon dioxide hydrogenation. Thanks to its abundance and cost-efficacy, cobalt can serve as an economical catalyst compared to noble-metal-based catalysts. In this work, we present a systematic comparison among different cobalt and cobalt oxide nanocomposites in terms of their efficiency as catalysts for carbon dioxide hydrogenation to methanol as well as how different supports can enhance their catalytic capacity. The oxygen vacancies in the cerium oxide act as carbon dioxide adsorption and activation sites, which facilitates a higher methanol production yield.

Aryl chlorides and bromides in the presence of NHC palladium hydroxo dimers of the type [{Pd(µ-OH)Cl(NHC)}2] (where NHC = IPr, SIPr, IMes, SIMes) undergo an efficient and selective Sonogashira cross-coupling with terminal acetylenes. For the coupling of 4-chlorotoluene with phenylacetylene TON = 560000 was observed. The procedure enables high-throughput and selective synthesis of a broad spectrum of unsymmetrically substituted 1,2-diarylacetylenes. Nearly a quantitative amount of HCl was detected within cross-coupling products. Water plays the role of the base and is regenerated in the process so that it does not have to be used in stoichiometric amounts (relative to the limiting reactant). Generation of the active Pd(0) complex proceeds via ethanol oxidation.

The work carried out first-principles calculations within the framework of density functional theory to study the structural stability of the CsSnI₃ compound and the influence of phase transitions on their electronic and optical properties. Using the GGA and SCAN functionals, the relaxed structures of the CsSnI₃ phases were obtained and their geometric characteristics were assessed. Using the Phonopy code based on VASP, calculations of phonon and thermodynamic properties were performed, and the temperatures of phase transitions of CsSnI₃ were determined. The temperature dependences of the thermodynamic parameters α-, β-, γ- and δ-phases of CsSnI₃ were analyzed. The trends in free energy, entropy, enthalpy, heat of formation energy and heat capacity were justified in terms of the pattern of changes in the total energy of the four phases of CsSnI₃ from VASP calculations. It is shown that at 0 K the non-perovskite structure of the CsSnI₃ compound (δ-CsSnI₃) is the most stable (followed by γ-CsSnI₃), and the tetragonal phase (β) is quite unstable, having the highest energy among the perovskite phases. It was revealed that at temperatures above 450 K the tetragonal phase becomes stable, and when the temperature drops, it transforms into the cubic phase (α-CsSnI₃). The phase transition between the β and γ phase of perovskite occurs in the range of 300-320 K, and at 320 K a black-yellow transformation of CsSnI₃ occurs in which the cubic phase (black perovskite) undergoes a phase transition to a non-perovskite conformation (yellow phase). The presence of temperature phase transitions between two orthorhombic phases of CsSnI₃ at 360 K was discovered, although direct transitions of the α⟷γ and γ⟷δ types have not yet been reported in any experiment, except for γ→δ transitions under the influence of moisture. Based on well-relaxed structures (from the SCAN calculations), the band gap widths for four CsSnI₃ phases were calculated and compared with experimental measurements. Electronic properties and Fermi level shifts as a result of phase transformations of CsSnI₃ were assessed using the HSE06 functional and machine learning prediction. The values of the complex dielectric constant and the refractive index of all phases of the CsSnI₃ were determined.

Effective sports training should be attuned to the athlete's specific conditionings and characteristics. In motor learning research, two often neglected factors that influence this resonance are the learner's athletic background and the structural diversity of exercises (e.g., relative similarity). This study examines the effects of three learning approaches (i.e., contextual interference (CI), differential learning (DL), and free-play control condition (CO)) on the parallel learning of Handball (HB), Volleyball (VB), and Basketball (BB) skills, considering participants' prior sport backgrounds. Forty-five males (15 HB, 15 VB, and 15 BB players) with a mean age of 22±1.4 years and at least 6 years of experience in the mastered discipline voluntarily participated in this study. A pre-post-retention test design including a 6-week-intervention program was employed. In terms of short-term (pre-post) gain, only the DL- group significantly improved their performance in both non-mastered disciplines (p=0.03 for the BB free-throw and p=0.05 for the HB shooting tests), with a trend (ES=0.53) towards an improvement in the performance of the mastered VB underarm-pass skill. In terms of relatively permanent gains, the CI group significantly improved their performances from pre- to retention-test only in the non-mastered BB free-throw skill (p=0.018). In contrast, the DL group significantly improved their performance at retention compared to the pre-test in both non-mastered BB (p=0.004) and HB (p=0.003) skills, with a trend (ES=0.4) towards improvement in the mastered VB test. In both short, and relatively permanent terms, higher composite score gains were observed in DL compared to CI (p=0.001 and 0.002) and CO (p=0.001 and <0.0001). In conclusion, the present findings provide additional support for the potential advantages of the DL model over those of CI. These findings can serve as the basis for tailored training and intervention strategies and provide a new perspective for addressing various issues related to individual and situational learning.

Dacomitinib is an irreversible epidermal growth factor receptor (EGFR) tyrosine kinase inhibitor indicated for the treatment of patients with advanced non-small cell lung cancer (NSCLC) and EGFR-activating mutations. Proton pump inhibitors decreased dacomitinib exposure. This anal-ysis summarizes the effect of H2RA on dacomitinib exposure. A within-patient comparison of steady-state trough concentrations (Ctrough,ss) of dacomitinib and its active metabolite and active moiety with and without concomitant use of H2RA was conducted using a linear mixed effects model with pooled data from 11 clinical studies in patients with NSCLC. An oral absorption PBPK model was constructed and verified using clinical PK data after a single dose of dacomitinib in healthy volunteers to estimate the effect of gastric pH altered by an H2RA on dacomitinib PK. The adjusted geometric mean of dacomitinib Ctrough,ss of dacomitinib parent, metabolite and active moiety following co-administration with H2RA was approximately 86%, 104% and 100% relative to that following dacomitinib 45 mg administration without H2RA (P>0.05). The PBPK modeling showed negligible change in dacomitinib Cmax and AUC over 0-24 hours after H2RA administra-tion, when compared with those administered dacomitinib alone. Co-administration of an H2RA with dacomitinib is not expected to have any clinically relevant effect on dacomitinib exposure.

In the seasonally frozen regions, during the grouting of prestressed bridge ducts in low-temperature environments, incompletely cured grout materials undergo volumetric changes due to the freeze-thaw cycling, resulting in structural cracks along the prestressing ducts of the bridge, thereby diminishing the bridge's operational lifespan. To investigate the frost heaving characteristics of grout materials under freeze-thaw cycles and propose potential enhancements, this study was devised to conduct frost heaving stress tests on grout materials. Through this research, we gained insights into how various additives affect the frost heaving stress characteristics of grout materials under freeze-thaw cycles. Incorporating analyses of free water content, setting time, compressive strength, as well as macroscopic examinations such as XRD and SEM, this study delves into the mechanisms for enhancing frost heaving characteristics of grout materials. Furthermore, it proposes a research approach that utilizes multiple admixtures to improve the frost heaving properties of grout materials. Through frost heaving stress tests and other macroscopic experiments, the study investigates the influence of these combined admixtures on frost heaving stress in grout materials and elucidates the underlying improvement mechanisms. The results indicate that reducing the water-cement ratio, incorporating calcium formate, sulfoaluminate cement, air-entraining agents, and carbamide all have a positive impact on mitigating frost heaving stress in grout materials. However, the improvement mechanisms differ, and employing a single measure alone is insufficient to effectively reduce frost heaving stress while meeting performance criteria such as compressive strength, setting time, and flowability. Free water content emerges as a crucial indicator determining the magnitude of frost heaving stress in grout materials, with 11.5% of free water content representing the critical threshold for frost heaving in grout materials. Utilizing composite admixtures can simultaneously decrease free water content, lower the freezing point of free water, and alleviate frost heaving deformation, resulting in more efficient reduction of frost heaving stress. When the admixture content reaches 9.9%, frost heaving stress is eliminated, and the comprehensive performance parameters including compressive strength, setting time, and flowability meet the specified requirements.

This research investigates the utilization of human driving models in autonomous vehicles, particularly in scenarios with minimal or no interactions with other vehicles. Human driving models provide valuable insights into driver behavior and play a crucial role in shaping the behavior of autonomous vehicles, enhancing their performance and user experience. The primary focus of the study is the creation of a planning model for autonomous vehicles when navigating roundabouts in the absence of traffic. This model seeks to emulate human driving behavior, ensuring predictability, safety, optimization of traffic flow, and adaptation to various roundabout geometries. To achieve this, the research introduces a trajectory model that takes into account geometric attributes and speed variations within roundabouts. The model is calibrated using empirical data and generalizes parameters through statistical regression methodologies. This model is referred to as "MRoundabout" and is evaluated for its consistency in generating plans that closely mimic human driving behavior within roundabouts. While the study presents a promising approach, it acknowledges limitations related to the model's reliance on geometric attributes and its inability to account for external factors like weather conditions. This research underscores the importance of bridging the gap between theoretical research and practical application, with the aim of enhancing safety and the overall user experience in real-world driving scenarios.

(1) Background: The synthesis of core-shell magnetic mesoporous nanoparticles (MMSN) from phase transfer process is usually performed at 100-250 mg scale. At the gram scale, nanoparticles without core or with multicore systems are observed. (2) Methods: Iron oxide core nanoparticles (IO) were synthesized through thermal decomposition procedure of -FeO in oleic acid. Phase transfer from chloroform to water was then performed in order to wrap IO with mesoporous silica shell through the sol-gel procedure. MMSN were then functionalized with DTPA, and used for the separation of metal ions. Their toxicity was evaluated (3) Results: The phase transfer pro-cedure was crucial to obtained MMSN at large scale. Three synthesis parameters were rigorously controlled: temperature, time and glassware. Homogeneous dispersion of MMSN at the gram scale was successfully obtained. After functionalization with DTPA, the MMSN-DTPA were shown to have a strong affinity for Ni ions. Furthermore toxicity was evaluated in cells, zebrafish and through seahorse metabolic assays, and the nanoparticles were found nontoxic. (4) Conclusions: We developed a method of preparation of MMSN at the gram scale. After function-alization with DTPA, the nanoparticles were efficient in metal ion removal and separation, fur-thermore, no toxicity was noticed up to 125 µg.mL-1 in zebrafish.

(1) Background: Most patients with mycosis fungoides (MF), a form of cutaneous T-cell lym-phoma (CTCL), develop relapsed/refractory (R/R) disease following front-line systemic therapy. This report describes treatment patterns and outcomes from the subpopulation with R/R MF. (2) Methods: This observational, retrospective, cohort study analysed patient records (1984–2016) from 27 clinical sites in Eurpe. Outcomes included treatments received, response to first-, second- and third-line treatment, overall survival (OS), and progression-free survival (PFS). (3) Results: Of 104 patients with MF, 100 received second-line and 61 received third-line therapy. Median (range) times from start of first-line therapy to first R/R MF and from first to second R/R MF were 11.2 (0.3–166.5) and 13.5 (0.0–174.6) months, respectively. Second-and third-line treatment options varied and comprised systemic therapies (85% and 79% of patients, respectively), radio-therapy (32% and 34%, respectively) and topical therapies (48% and 36%, respectively). Median (95% confidence interval [CI]) OS from the diagnosis of first R/R MF was 11.5 (6.5–not reached [NR]) years and was higher with non-chemotherapy (NR) versus chemotherapy (6.5 years); es-timated median PFS (95% CI) from the time of first R/R MF was 1.3 (1.0–2.1) years. (4) Conclu-sion: High rates of R/R disease were observed after second- and third-line treatments in this re-al-world cohort, with longer median OS in patients receiving non-chemotherapy versus chemo-therapy. Following the standard management of MF and using recently approved targeted therapies can help improve patient outcomes in advanced-stage MF.

An inorganic solid electrolyte is the most favorable candidate for replacing flammable liquid electrolytes in lithium batteries. Lithium Lanthanum Zirconium Oxide (LLZO) is considered as a promising solid electrolyte due to its safe operating potential window (0-5V) combined with its good electrochemical stability. In this work, 250 g batches of pre-sintered Tadoped (Li7La3Zr1.6Ta0.4O12, TaLLZO) were synthesized for bulk production of dense LLZO electrolyte. A simple two-step thermal treatment process was developed. The first thermal step at 950 °C initiates nucleation of LLZO carefully controlling process parameters such as heating atmosphere, temperature and dopant concentration. In the second thermal step at 1150 °C, sintered discs were obtained as solid electrolytes, with relative densities of 96%. X-ray diffraction analysis confirmed the phase purity of the sintered TaLLZO disc, and refined data was used to calculate the lattice parameter (12.944 Å). Furthermore, the presence of the Ta dopant in the disc was confirmed through X-ray photoelectron spectroscopy (XPS) analysis. The ionic and electronic conductivity values of TaLLZO disc were 104 S cm-1 and 10-10 S cm-1, respectively. These values confirm that the prepared (Ta-LLZO) discs exhibit ionic conductivity while being electronically insulating, being suitable for use as solid electrolytes with the requisite electrical properties.

Tantalum oxide thin films are deposited by DC reactive magnetron sputtering from a tantalum metallic target and oxygen as reactive gas. The reactive gas pulsing process (RGPP) is implemented to produce TaOx compounds with tunable chemical compositions. The argon mass flow rate is maintained constant whereas that of the oxygen gas is pulsed during the deposition. A constant pulsing period T = 10 s is used and the introduction time of the oxygen gas, namely the tON injection time, is systematically changed from 0 to 100 % of the pulsing period T. As the tON injection time increases, the chemical composition of as-deposited TaOx films is continuously changed from pure metallic tantalum to the over-stoichiometric Ta2O5 material. Analysis of the crystallographic structure by X-ray diffraction shows that the films adopt the body-centered cubic structure (metallic Ta) for the lowest tON injection time values (oxygen stoichiometry x &lt; 1.0) and become amorphous for the longest tON injection times. It is shown that the tON injection time is a key parameter to produce either homogeneous tantalum oxides, or periodic Ta/TaOx multilayers with alternations close to 3 nm. Similarly, optical transmittance spectra of the film/glass substrate system are recorded in the visible region and the electrical conductivity of the films is measured vs. temperature. Both exhibit a gradual evolution from metallic (300K = 8.17105 S m-1 with a null optical transmittance in the visible range) to semi-conducting (300K = 1.97103 S m-1 with a semi-transparent behavior) and finally to dielectric properties (300K &lt; 10-5 S m-1 for interferential films) as a function of the oxygen concentration in the films.

This article presents the possibilities of using ferrite absorption material for shielding rooms with medical devices in order to additionally protect them against the limits of the electric component of the E field, which are up to 61 V/m. These values may appear in connection with the currently launched 5G system operating in the high-band frequency range, i.e. 28 GHz and 38 GHz, and may cause negative effects on the operation of medical devices. The possibilities of using ferrite absorption material for shielding rooms with medical devices were determined based on the results of measurements of the electrical properties of the ferrite material performed using two methods: the reflection method and the free space method. In the article, the complex electrical permittivity and complex magnetic permeability were determined for a ferrite plate based on measurements of the reflection coefficient and the transmission (attenuation) coefficient. The presented calculation and measurement results were used to show the properties of the ferrite material in the frequency range from 15 GHz to 45 GHz and to show the possibility of using it for shielding rooms as a material absorbing electromagnetic waves in this frequency range.

This review article deals with the pathways of cellular and global molybdate distribution in plants, especially with a full overview for the model plant Arabidopsis thaliana. In its oxidized state as bioavailable molybdate, molybdenum can be absorbed from the environment. Especially in higher plants, molybdenum is indispensable as part of the molybdenum cofactor (Moco), which is responsible for functionality as a prosthetic group in a variety of essential enzymes like nitrate reductase and sulfite oxidase. Therefore, plants need mechanisms for molybdate import and transport within the organism, which is accomplished via high-affinity molybdate transporter (MOT) localized in different cells and membranes. Two different MOT-families were identified. Especially legumes like Glycine max or Medicago truncatula have an increased numbers of MOT1-family members for supplying their symbionts with molybdate for nitrogenase activity. In Arabidopsis thaliana especially, the complete way of molybdate through the plant is traceable. Not only the uptake from soil by MOT1.1 and its distribution to leaves, flowers and seeds by MOT2-family members was identified, but also inside the cell the transport trough the cytoplasm and the vacuolar storage mechanisms depending on glutathione were described. Finally, supplying the Moco biosynthesis complex by MOT1.2 and MOT2.1 was demonstrated.

Compared to tin lead alloys, lead-free tin alloys have lower toxicity, making them more widely used. In this study, Sn-20Bi-0.3Al-xY solders alloys were prepared. The effects of the addition of Y on its microstructure, micro-hardness, wettability and mechanical properties was investigated. The result showed that the addition of Y had significant effect on the refinement of Sn-20Bi-0.3Al-xY. From the spreading tests results, Y increased the wettability of the solders, however when the fraction of Y gradually increased, the wettability reduced. The ultimate tensile and hardness of Sn-20Bi-0.3Al-xY solders alloys were increased as the content of Y increasing.

Composite polymolecular separation membranes were prepared by combining multi-branched ZIF-L with high porosity electrospinning nanofibers PI. Meanwhile, PDA and PEI were introduced into the membrane in order to improve its adhesion. The new membrane is so called “PI@PDA@PEI/ZIF-L-4” composite membrane; compared with PI@PDA@PEI/ZIF-8 composite membrane, the new membrane’s filtration rates for heavy metal ions such as Cd2+, Cr3+ and Pb2+ were increased by 7.0%, 6.6% and 9.3%, respectively. Furthermore, the new membrane has a permeability up to 1,140.0 L·m−2·h−1·bar−1, and were presenting a very stable performances after four repeated uses. The separation mechanism of PI@PDA@PEI/ZIF-L composite membranes was further analyzed in order to provide a base support for producing separation membranes with high barrier rate and high flux.

Modern imaging strategies are paramount to studying living systems such as cells, bacteria, and fungi and their response to pathogens, toxicants, and nanomaterials as modulated by exposure and environmental factors. The need to understand the processes and mechanisms of damage, healing and cell survivability of living systems continues to motivate the development of alternative imaging strategies. Of particular interest is the use of label-free techniques that minimize interference of biological processes by foreign marking substances and reduce intense light exposure and potential photo-toxicity effects. This review focus on the potential synergic capabilities of atomic force microscopy (AFM) as a well-developed and robust imaging strategy with demonstrated applications to unravel intimate details in biomedical applications, with the label-free, fast, and enduring Holotomographic Microscopy (HT) strategy. We first review the operating principles that form the basis for the complementary details provided by these techniques regarding the surface and internal information provided by HT and AFM is essential and complimentary for the development of several biomedical areas studying the interaction mechanisms of nanomaterials with living organisms. First, AFM can provide superb resolution on surface morphology and biomechanical characterization. Second, the quantitative phase capabilities of HT enable superb modeling and quantification of the volume, surface area, protein content, and mass density of the main components of cells and microorganisms, including morphology of cells in microbiological systems. These capabilities result from directly quantifying refractive index changes without requiring fluorescent markers or chemicals. As such, HT is ideally suited for long-term monitoring of living organisms in conditions close to their natural settings. We present a case-based review of the principal uses of both techniques and their essential contributions to nanomedicine and nanotoxicology, emphasizing cancer and infectious disease control. The synergic impact of the sequential use of these complementary strategies provides a clear drive for adopting these techniques as interdependent fundamental tools.

Hip replacement has significantly improved the quality of life of patients with symptomatic hip osteoarthritis. Metal-on-metal (MoM) bearings have been used with conventional total hip re-placement (THR) for several decades with promising results from early applications. Wear and corrosion of these implants may lead to a release of metal products into surrounding tissue and body fluids. From the 1980s onwards, the search for increasingly better coupling materials with low levels of wear led to the rise of hard-on-hard couplings such as ceramic-on-ceramic (CoC). The latter is currently the coupling with the longest known duration and with a wear rate close to zero. MoM coupling has been for a long time the most significative alternative, but systemic and local complications linked to the release of chromium and cobalt ions, determine the withdrawn from the market. One other alternative proposed over the time has been Ceramic-on-Metal (CoM) bearing. Preliminary results have been described as favourable, but due to the failures of metal on metal it has been withdrawn from the market, without causing significant clinical complications. In this narrative review, we analysed risks and benefits associated with the implantation of hybrid hard-on-hard bearings, such as CoM.

Objectives: This study aimed to assess the impact of a predictive model for detecting extracapsular extension on pathology (pECE+) on biochemical recurrence-free survival (BCRFS) within 4 years after robotic-assisted radical prostatectomy (RARP). Methods: Retrospective data analysis from a single center between 2015 to 2022. Variables under consideration included prostate-specific antigen (PSA) levels, patient age, prostate volume, MRI semantic features and Gleason score (GS). We also assessed the influence of pECE+ and positive surgical margins on BCRFS. using the Kaplan-Meier survival function and Cox regression model were assessed. Additionally, we analyzed the MRI features on BCR (biochemical recurrence) in low/intermediate risk patients. Results: 177 participants with a follow-up exceeding 6 months post-RARP were included. The 1-year, 2-year, and 4-year risks of BCR after curative prostatectomy were 5%, 13%, and 21%, respectively. The survival analysis showed that adverse MRI features as macroscopic ECE on MRI (mECE+), capsular disruption, high tumor capsular contact length (TCCL), GS≥8, positive surgical margins (PSM), and pECE+ on pathology were risk factors for BCR. In low/intermediate-risk patients (pECE- and GS &lt;(4+4)) the presence of adverse MRI features, has been shown to increase the risk of BCR. Conclusions: The study highlights the importance of incorporating predictive MRI features for detecting extracapsular extension pre-surgery in influencing early outcomes and clinical decision-making; mECE+, TCCL, capsular disruption, and GS≥8 based on pre-surgical biopsy were independent prognostic factors for early BCR. The presence of adverse features on MRI can assist in identifying low/intermediate-risk patients who would benefit from closer monitoring.

It is important to develop new antibacterial drugs since the emergence of bacterial resistance to available antibiotics. Metal nanoparticles have the potential to combat antibiotic resistance and are effective antibacterial agents. Here, we demonstrate the biogenic production of zinc nanoparticles using Rhododendron arboreum stem bark. The biosynthesized ZnNPs were characterized through different analytical techniques such as UV-vis, FTIR, EDX, SEM, and XRD. Clinical isolates such as E. coli, S. aureus, and K. pneumonia were used to check the antibacterial efficacy of the biosynthesized zinc nanoparticles. The MIC and MBC values against K. pneumonia, S. aureu, and E. coli were found to be 34±0.21 and 11.71±0.47, 47±0.11 and 23.86±0.84 and 94±0.18 and 40.43±0.16 µg/mL, respectively. It dramatically decreased the integrity of the cell membrane and markedly increased the permeability of both inner and outer membranes. The green synthesized ZnNPs have good catalytic activity. It degraded 65% of methyl orange dye within 6h when the mixture was kept in direct sunlight, thus demonstrating good photodegradation potential and can be employed as a good photocatalyst. According to these results, biosynthesized zinc nanoparticles could be a potential therapy option for controlling bacterial pathogenesis and an effective photocatalyst for the elimination of hazardous water contaminants.

Background: Glioblastoma is the most common primary brain neoplasm in adults, with still a poor prognosis despite a constant effort to improve patients’ survival. Some neuroradiological volumetric parameters seem to play a predictive role on Overall Survival (OS) and Progression Free Survival (PFS). The aim of this study is to analyze the impact that the volumetric areas of contrast-enhancing tumor and perineoplastic edema have on survival of patients treated for glioblastoma; Methods: A series of 87 patients who underwent surgery was retrospectively analyzed; OS and PFS were considered as the end points of the study. For each patient a multidisciplinary revision was conducted in collaboration with the Neuroradiology and Neuro-Oncology board. A manual and semi-automatic measurement were adopted to perform the radiological evaluation: contrast Enhancement Preoperative (CE-PTV) and Postoperative Tumor Volume (CE-RTV), Edema/Infiltration Preoperative (T2/FLAIR-PV) and Postoperative Volume (T2/FLAIR-RV); necrosis volume inside the tumor (NV); total tumor volume, including necrosis (TV); Results: The median OS value was 9 months and the median PFS value was 4 m; the mean values were respectively 12,3 m and 6,9 m. Multivariate analysis showed that the OS related factors were: adjuvant chemo-radiotherapy (p &lt; 0,0001), CE-PTV &lt; 15 cm³ (p=0,03), surgical resection &gt; 95% (p=0,004) and the presence of a “pseudo-capsulated” radiological morphology (p=0,04); Conclusions: maximal safe resection is one of the most relevant predictive factors for patients’ survival. The semi-automatic pre-operative MRI evaluation could play a key role in prognostically categorizing these tumors.

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.

Trans-arterial radioembolization (TARE) is a form of radiation therapy performed for hepatocellular carcinoma (HCC) via selective intra-arterial injection of Yttrium-90 loaded microspheres. This was a multicenter retrospective study of consecutive patients with HCC who underwent TARE between July 2009 and May 2019. Using pre-treatment computed tomography imaging, the total cross-sectional area (cm2) of the abdominal skeletal muscle at the third lumbar vertebra was measured. The skeletal muscle index (SMI) was calculated by normalizing the muscle area to patient height. In total, 347 patients (median age, 65 years; 284 male) were included in the study. A total of 108 (31.1%) patients had portal vein tumor thrombus (PVTT) and 126 (36.3%) were classified as sarcopenic. The median overall survival (OS) was 28.1 months (95% CI, 24.8-35.7) and median progression-free survival was 8.0 months (95% CI, 6.4-9.4). Multivariate Cox regression analysis revealed that sarcopenia (hazard ratio [HR], 1.36; 95% CI, 1.00-1.85, p = 0.05), PVTT (HR, 1.82; 95% CI, 1.33-2.49, p &lt; 0.01), alpha-fetoprotein (AFP) (≥200 ng/mL) (HR 1.41; 95% CI, 1.04-1.92, p = 0.03), and albumin-bilirubin grade (2-3) (HR 1.74; 95% CI, 1.24-2.43, p &lt; 0.01) were independently associated with poor OS. TARE provided favorable long-term outcomes for patients with advanced HCC. Pre-treatment sarcopenia independently associated with survival, suggesting its utility as a surrogate biomarker for identifying TARE candidates.

New complexes of manganese(II) hexafluoroacetylacetonate [Mn(hfac)2] with 2-(1-R-3-pyrazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (R = CHF2, CH2CH2F, CH2CHF2 or CH2CF3) were synthesised and characterised structurally and magnetically. All complexes were prepared under similar conditions. Nonetheless, their crystal structures were considerably different. Depending on the structure of fluorinated alkyl substituent R, the complexation reaction led to complexes of three types: chain-polymeric complexes with the head-to-head or head-to-tail motif and complexes of molecular structure. All complexes show strong antiferromagnetic behaviour in a high-temperature region (150−300 K) and weak ferro- or antiferromagnetic exchange interactions at low temperatures. The stronger antiferromagnetic exchange, –101.7 ± 1.5 or –136 ± 10 cm–1, –82.3 ± 1.3 cm–1 and –87.4 ± 1.3 cm–1, was attributed to the magnetic interaction in three- or two-spin clusters: {&gt;N∸O–Mn2+–O∸N&lt;} or {&gt;N∸O–Mn2+}, respectively. The weaker antiferromagnetic interaction, –0.005, between three-spin clusters or ferromagnetic interactions, 0.18–0.81 cm–1, between two-spin clusters are realised through the pyrazole ring or intermolecular contacts.

The interactions of metal ions with fulvic acids resulted in changes in the particle size and charge. Particle size distribution was trimodal for fulvic acids, bimodal for fulvic complexes with calcium and magnesium, and copper-fulvic complexes had only one size fraction. The compensation of negative charge of carboxylic and phenolic functional groups by positive charged metal ions resulted in the increase in zeta potential which was getting closer to zero in the case of copper-fulvic complexes. However, all metal humic complexes behaved as colloidally unstable which resulted in visually observable sedimentation. Calorimetric measurements provided positive values of changes in enthalpy which indicated endothermic processes. In contrast quantum chemical calculations as well as experiments with model compounds provided negative values indicated exothermic processes. Changes in Gibbs energy were determined as negative and changes in entropy as positive which meant spontaneous processes.

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.

Determination of the fetal gender in the first trimester is important in twin pregnancy cases of familial X-linked genetic syndromes and helps determine chorionicity. We assessed and compared the accuracy of first-trimester ultrasound scans, and circulating cell-free fetal DNA (cffDNA) performed by non-invasive prenatal screening (NIPS) in determining fetal gender in the first trimester of twin pregnancies. For this purpose, we enrolled prospectively pregnant women with twin during the first trimester, gestational week (GA) 11-13. The fetal gender was determined using both ultrasound scans and cffDNA screening. Both results were compared to the newborn gender at delivery. A total of 113 women with twin pregnancies were enrolled. There was 100% sensitivity and specificity in Y chromosome detection using cffDNA. The accuracy of gender assignment using ultrasound in any first-trimester scans was 79.7%. Accuracy level increased from 54.2% in CRL 45-54 mm to 87.7% in CRL 55-67 mm and 91.5% in CRL 67-87 mm. Male fetuses had significantly higher chances of a gender assignment error compared to female fetuses, odds ratio = 23.57 (CI 7.356 - 75.66). This is the first study that compared the accuracy of gender determination in the first trimester by cffDNA and by ultrasound scanning in twin pregnancy. It was concluded that the cffDNA is highly sensitive and specific in determining the presence of the Y chromosome in twin pregnancies in the first trimester. Between CRL 67-87 mm, ultrasound scanning offers a highly accurate determination of fetal gender in twin pregnancies. Larger cohorts of multi-center studies are warranted.