Since its initial development in the 1970’s by Phil Burke and his collaborators, the R-matrix theory and associated computer codes have become the de facto approach for the calculation of accurate data for general electron-atom/ion/molecule collision and photoionization processes. The use of a non-orthonormal set of orbitals based on B-splines, now called the B-spline R-matrix (BSR) approach, was pioneered by Zatsarinny. It has considerably extended the flexibility of the approach and improved particularly the treatment of complex many-electron atomic and ionic targets, for which accurate data are needed in many modelling applications for processes involving low-temperature plasmas. Both the original R-matrix approach and the BSR method have been extended to the interaction of short, intense electromagnetic (EM) radiation with atoms and molecules. Here we provide an overview of the theoretical tools that were required to facilitate the extension of the theory to the time domain. As an example of a practical application, we show results for two-photon ionization of argon by intense short-pulse extreme ultraviolet radiation

Background: This study stands as a pioneer in the histological evaluation of the biological behavior of a novel implant design featuring decompressive cervical blades. Hence, the aim of the present study was to evaluate the healing outcome in cortical regions at where decompressive protocols were adopted using implants equipped with blades. Materials and methods: Blades with varying diameters were integrated into the coronal portion of the implant to prepare the cortical region of rabbit tibiae. The blade diameters differed from the implant collar by the following amounts: control group (0 µm), +50 µm, and +200 µm. Results: No marginal bone loss was detected. Instead, all implants exhibited new bone formation in the coronal region. Complete closure was observed in the CG-0 group, as well as in the TG-50 and TG-200 groups, despite the presence of marginal gaps without primary bone contact at installation. In the apical region, most implants breached the cortical layer. Nevertheless, new bone formation in this region completely closed the osteotomy, effectively isolating the internal environment of the tibia from the external. Conclusions: The use of a blade attached to the implant body enabled precise preparation of the cortical layer, allowing for controlled decompression in the targeted area. This technique resulted in optimal osseointegration with no loss of marginal bone, and complete restoration of marginal gaps ranging from 0 µm to 200 µm.

The distribution of tiny sensors over a specific area was first proposed in the late 1990s as a concept known as Smart Dust. Several efforts focused primarily on computing and networking capabilities but quickly ran into problems related to power supply, cost, data transmission, and environmental pollution. To overcome these limitations, we propose using paper-based (confetti-like) chemosensors that exploit the inherent selectivity of chemical reagents, such as colorimetric indicators. In this work, cheap and biodegradable passive sensors made from cellulose could successfully indicate the presence of hazardous chemicals, e.g., strong acids, by a significant color change. A conventional color digital camera attached to a drone could easily detect this from a safe distance. The collected data was processed to define the hazardous area. Our work presents a combination of the smart dust concept, chemosensing, paper-based sensor technology, and low-cost drones for flexible, sensitive, economical, and rapid detection of hazardous chemicals in high-risk scenarios.

The affinity constant, also known as the equilibrium constant, binding constant, equilibrium association constant, or the reciprocal value, the equilibrium dissociation constant (K_d), can be considered as one of the most important characteristics for any antibody-antigen pair. Many methods based on different technologies have been proposed and used to determine this value. However, since a very large number of publications and commercial datasheets do not include this information, significant obstacles in performing such measurements seem to exist. In other cases where such data are reported, the results have often proved to be unreliable. This situation may indicate that most of the technologies available today require a high level of expertise that does not seem to be available in many laboratories. In this paper, we present a simple approach based on standard immunoassay technology that is easy and quick to perform. It relies on the effect that the molar IC₅₀ approaches the K_d value in the case of infinitely small concentrations of the reagent concentrations. A two-dimensional dilution of the reagents leads to an asymptotic convergence to K_d. The approach has some similarity to the well-known checkerboard titration used for the optimization of immunoassays. A well-known antibody against the FLAG peptide, clone M2, was used as a model system and the results were compared with other methods. This approach could be used in any case where a competitive assay is available or can be developed. The determination of an affinity constant should belong to the crucial parameters in any quality control of antibody-related products and assays and should be mandatory in papers using immunochemical protocols.

Introduction. Autopsy is a medical procedure that consists of the corpse’s examination to determine the cause of death and obtain information on pathological conditions or injuries present in the body. In recent years there has been a reduction in hospital autopsies and an increase in forensic autopsies. Material and methods. A retrospective observational study was conducted on the reports of all the 645 hospital autopsies performed at Polyclinic of Bari from 2006 to 2021.Results. Group A, 2006-2009, 174 cases were studied: 58% male, 58% adults, 55% neonatology, pulmonary disease was the cause of death in 23%, and 55% of discrepancy between clinical and autopsy diagnosis. Group B, 2010-2013, comprised 119 cases: 52% male, 46% infants, 48% neonatology, pulmonary disease was the cause of death in 25%, and 56% of discrepancy between clinical and autopsy diagnosis. Group C, 2014-2017, comprised 168 cases: gender equality, 37% infants, 25% gynecology, pulmonary disease was the cause of death in 24%, and 58% of discrepancy between clinical and autopsy diagnosis. Group D, 2018-2021 comprised 184 cases: 56% male, 38% adult, 32% gynecology, pulmonary disease was the cause of death in 27%, and 58% discrepancy between clinical and autopsy diagnosis.Conclusion. The study of hospital autopsies at the Polyclinic of Bari shows that the discrepancy between clinical and autopsy diagnosis is around 56.75%. Thus, the hospital autopsy is helpful in the modern age, especially for diagnosing fetal and neonatal diseases.

In this paper glass crystallization behavior of 50ZnO:47B2O3:3Nb2O3:0.5Eu2O3 (G-0h) glass has been investigated in detail by DSC, XRD and TEM analysis. The luminescent properties of resulted glass-ceramics were also investigated. By XRD and TEM analysis crystallization of several crystalline phases have been proved (α-Zn3B2O6, β-Zn3B2O6 and ZnNb2O6). By calculating of crystal parameters it was found that europium ions are successfully incorporated in the β-Zn3B2O6. Photo-luminescent spectra show an increased emission in the resulting glass-ceramic samples as compared with the parent glass sample because of the higher asymmetry of Eu3+ ions in the crystalline phases obtained. It was established that the optimum emission intensity is registered for glass-ceramic sample obtained after 25 hours heat treatment of the parent glass.

The ability of thermoresponsive polymers to respond to temperature with a reversible conformational change makes them promising ‘smart’ materials for solutions in medical and biotechnological applications. In this work, two such polymers and structural isomers were studied: poly(N-isopropyl acrylamide) (PNiPAm) and poly(2-isopropyl-2-oxazoline) (PiPOx). We compare the critical solution temperatures (CST) of these polymers in D2O and H2O in the presence of Hofmeister series salts, as results obtained under these different solvent conditions are often compared. D2O has a higher dipole moment and electronegativity than H2O, which could significantly alter the CST transition. We used two complementary methods to measure the CST, dynamic light scattering (DLS) and differential scanning calorimetry (DSC), and found that the CST decreased significantly in D2O compared to H2O. In the presence of highly concentrated kosmotropes, the CST of both polymers decreased in both solvents. The influence of the kosmotropic anions was smaller than the water isotope effect at low ionic strengths but considerably higher at physiological ionic strengths. However, the Hofmeister anion effect was quantitatively different in H2O than in D2O, with the largest relative differences observed for Cl-, where the CSTs in D2O decreased more than in H2O measured by DLS but less by DSC. PiPOx was more sensitive than PNiPAm to the presence of chaotropes. It exhibited much higher transition enthalpies and multistep transitions, especially in aqueous solutions. Our results highlight that measurements of thermoresponsive polymer properties in D2O cannot be compared directly or quantitatively to application conditions or even measurements performed in H2O.

: When municipal solid waste (MSW) is landfilled, it begins to decompose under anaerobic conditions and is formed landfill gas is dominated by methane (CH4) and carbon dioxide (CO2). Reducing methane emissions is essential in the fight against climate change. It must be implemented at global and European levels, as set out in 2030 in the impact assessment of the climate goals plan. This assessment states that to achieve the goal by 2030 and to reduce greenhouse gas emissions by at least 55%, the methane emissions must be reduced, considering the goals of the Paris Agreement. The Glasgow Climate Pact includes a global mitigation target of 2030 year: to reduce CO2 emissions by 45%, the emissions of methane and other greenhouse gases. For that purpose, looking for new, more advanced ways of managing such waste is necessary. The main objective of the experimental study was to evaluate the influence of aeration, probiotic introduction, and water supply on the production of landfill gases (CO2, CH4, N2, H2, etc.) in the different fifth landfills’ models during the management of MSW and to propose the best solutions for reducing environmental pollution. The results of the research showed that the first and second models of landfills, using only anaerobic conditions, can be used for the treatment of MSW for the production of biogas (CH4, CO2), as up to 40–60% of it was released during the 120-experiment period. The third landfill model can be applied in old, already closed landfills, where rapid stabilization and aeration of MSW are required to minimize pollutant emissions (N2, etc.) and unwanted odors and shorten biodegradation processes. The results of the fourth and fifth landfill models, in which aerobicanaerobic conditions were applied, showed that the developing nitrification-denitrification processes resulted in complete nitrogen removal (from 20% to 0%), and overall waste stabilization improved the biodegradation of the MSW. Later, relatively good (on average 30%) results of biogas (CH4, CO2) emissions are achieved during anaerobic conditions formation results. Summarizing all experiment results of all landfill models for further evaluation of the processes, all models can be applied in real practice depending on where they will be used and what result they want to achieve.

Genetic similarity determines the extent to which two genotypes share common genetic material. It can be measured in various ways, such as comparing DNA sequences, proteins, or other genetic markers. The significance of genetic similarity is multifaceted and encompasses various fields, including evolutionary biology, medicine, forensic science, animal and plant breeding, and anthropology. Genetic similarity is an important concept with wide application across different scientific disciplines. In the presented study, six measures for calculating genetic similarity were compared: Euclidean, Jaccard, Kulczyński, Sokal and Michener, Nei, and Rogers. The research material included 21 rapeseed genotypes (ten interspecific Brassicaceae hybrids of F2 generation, and 11 of their parental forms) and 146 alleles, obtained using 21 ISSR molecular markers. The results indicate that the research material was divided into two identical groups using any of the proposed methods, despite differences in the values of genetic similarity coefficients. Two of the presented measures of genetic similarity (Sokal and Michener, and Euclidean) were the same.

Crystalline silver thin layers were obtained by high-energy pulsed laser ablation without heating of the deposition substrate. The fluid Plateau-Rayleigh (PRI), Rayleigh – Taylor (RTI) and Richtmyer – Meshkov (RMI) instabilities, as well as crown splash induced during pulsed laser deposition (PLD) in high energy regime, resulting in ring and pearl shaped structures, offer the benefit of increased sorption surface. These morphological structures obtained for the silver thin layers make them of interest for catalytic applications. The study presented with this work addresses both the fundamental and applied issues on the morphological structures obtained for the silver thin layer and their catalytic function in organic processes. In this sense, the catalytic action of the thin silver layer was highlighted by modifications of the Reactive Blue 21 dye (C.I.) in aqueous solution with sodium bicarbonate. Specific investigations and analyzes were carried out by electron microscopy and elemental analysis (SEM-EDX), atomic force microscopy (AFM) and profilometry, mass spectrometry, ablation plasma diagnosis, diffractograms (XRD), as well as IR spectroscopy (FTIR). In addition to the experimental investigation and analyzes, simulation of the ionization energy threshold was conducted in COMSOL for complementary evaluation on the involved processes and phenomena.

Arylmagnesium and -calcium reagents are easily accessible, however, ether degradation processes limit the storability especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C₆H₃-2,6-(CH₂PPh₂)₂}₂] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo- (1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of THF yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf)₃Ca(X)(µ-O₂PPh₂)]₂ [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P-C bonds. Ether adducts of calcium halides [such as [(dme)₂(thf)CaBr₂] (4)] form supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.

Abstract: Peptide pools composed of short amino acid sequences have proven to be versatile tools in various research areas and clinical applications. They are powerful tools for epitope mapping, immunotherapy, and vaccine development. Their importance lies in their ability to map complex protein structures, enabling a comprehensive understanding of immune responses and facilitating the identification of potential therapeutic agents. The application of peptide pools also extends to the field of personalized medicine, offering tailored solutions for diseases such as cancer and infectious diseases. Peptide pools are complex mixtures of immunostimulatory antigens primarily intended for T-cell stimulation. They are commercially available in many different compositions and variants. However, unlike other reagents that consist of only one or a few compounds, peptide pools are highly complex products with limited stability. This makes their quality control a major challenge. Quantitative peptide analysis usually requires sophisticated methods, in most cases isotope-labeled standards and reference materials. None of these are routinely available for these products. Synthesis and purification of all labeled peptides might be required. Usually, this approach would be prohibitively laborious and expensive. Therefore, an approach is needed to provide a practical and feasible method for quality control of peptide pools. With insufficient quality control, the use of such products could lead to incorrect experimental results, which would worsen the well-known reproducibility crisis in the biomedical sciences. Here we propose the use of ultra-high performance liquid chromatography (UHPLC) with two detectors, a standard UV detector (at 214 nm) for quantitative analysis and a high-resolution mass spectrometer (HRMS) for identity confirmation. To be cost-efficient and fast, quantification and identification are performed in one chromatographic run. An optimized protocol is shown, and different peak integration methods are compared and discussed. This work was performed using a peptide pool known as CEF, which consists of 32 peptides derived from cytomegalovirus (CMV), Epstein-Barr virus (EBV) and influenza virus, ranging from 8 to 12 amino acids in length.

The reaction between cadmium nitrate tetrahydrate and N,N'-bis(pyridin-3-ylmethyl)oxalamide (L) in 1:3 molar ratio in water/acetonitrile (1:6 v/v) mixture afforded single crystals of compound 1 suitable for X-ray diffraction analysis. Compound 1 consists of the coordination polymer (CP) [[Cd(L)2(H2O)2](NO3)2·4H2O]∞, in which CdII ions are bridged by the neutral L antiperiplanar N-ligands in a wavy ribbon fashion developing along the c-axis. Two trans-disposed water molecules complete the pseudo-octahedral coordination geometry of the metal ion. The crystal packing of 1 revealed the interplay between π-π stacking interactions and an intricate hydrogen-bonded network involving oxalamides, nitrates and water molecules. The donor properties of L and the intermolecular interactions in compound 1 are interpreted based on hybrid-DFT calculations.

A dioxomolybdenum catalyst [(MoO2Cl2-O-MoO2Cl2)(L)] (1) (with L (1S,2S)-N,N´-bis(2-pyridinecarboxamide)-1,2-cyclohexane) was prepared and used as catalyst for the desulfurization of a multicomponent model fuel containing the most refractory sulfur compounds in real fuels. This complex showed to have a high efficiency to oxidize the aromatic benzothiophene derivative compounds present in fuels, mainly using a biphasic 1:1 model fuel/MeOH system. This process conciliates catalytic oxidative and extractive desulfurization, occurring the oxidation of the sulfur compounds in the polar organic solvent. The oxidative catalytic performance of (1) showed to be influenced by the presence of water in the system. Using 50% aq. H2O2 it was possible to reuse the catalyst and the extraction solvent MeOH during ten consecutive cycles without loss of desulfurization efficiency.

Stress during a pandemic increased the risk of alcohol consumption, which may require pharmacological management. The characteristics of emergency calls for alcohol-related issues for patients pharmacologically treated, admitted to, or not admitted to the emergency department (ED) were analyzed. An observational single-center retrospective study was conducted from January 1, 2018 to December 31, 2021, and divided into 2-year periods (2018–2019 and 2020–2021). This study focused on calls to one of the EDs of seven hospitals in the Bari (Italy) metropolitan area for patients requiring emergency services (ES) who were either admitted or not admitted, due to their refusal. A 30% reduction in emergency calls for alcohol-related issues and a 41.17% reduction in calls for patients who refused to be admitted to the ED were observed during the pandemic. During the pandemic, a reduced rate of pharmacological treatment for calls coded green (non-critical), and an increase in calls coded yellow (fairly critical) and red (very critical) were recorded. Metadoxine was administered in almost all alcohol-related emergencies, primarily in conjunction with drugs acting on the gastrointestinal tract, irrespective of age, the period considered, and whether patients were admitted or not admitted to the ED. ES is the first and only out-of-hospital service encountered by numerous patients with alcohol-use disorders who refuse to be admitted to the ED. These patients should be directed by ES personnel to a multidisciplinary program to receive treatment for drinking, improve their quality of life, and reduce sanitation costs.

Visible-light photocatalysis, particularly in its application to organic synthesis, has experienced a big renaissance in the past decade. The rational design of new photocatalysts with designed and improved photocatalytic properties, that at the same time circumvents the necessity of using scarce and toxic transition metals, will predictably play a key role in photocatalysis in the next few years. Although free-base porphyrins were identified some years ago as a promising, easily accessible and easily tunable class of organic photoredox catalysts, a systematic study on the effect of the electronic nature and of the position of the substituents on both the ground-state and the excited-state redox potentials of these compounds is still lacking. We have prepared a set of known functionalized derivatives of meso-tetraphenyl porphyrin containing different substituents either in one of the meso-positions or at a beta-pyrrole carbon and we have determined their ground- and (singlet) excited-state redox potentials. This survey has led us to conclude that the introduction of a carbonyl group at the beta-pyrrolic position strongly increases the facility of the monoelectronic reduction of the porphyrin both in the ground state and in the singlet excited state. We have also prepared a second set of four previously unknown benzoyl derivatives of meso-tetraphenylporphyrin, and we have confirmed the validity of our conclusions.

We present a novel method for interpolating univariate time series data. The proposed method combines multi-point fractional Brownian bridges, a genetic algorithm, and Takens’ theorem for reconstructing a phase space from univariate time series data. The basic idea is to first generate a population of different stochastically interpolated time series data, and secondly, to use a genetic algorithm to find the pieces in the population which generate the smoothest reconstructed phase space trajectory. A smooth trajectory curve is hereby found to have a low variance of second derivatives along the curve. For simplicity, we refer to the developed method as PhaSpaSto-interpolation, which is an abbreviation for phase-space-trajectory-smoothing stochastic interpolation. The proposed approach is tested and validated with a univariate time series of the Lorenz system, five non-model data sets and tested against a cubic spline interpolation and a linear linear interpolation. We find that the criterion for smoothness guarantees low errors on known model and non-model data. Finally, we interpolate the discussed non-model data sets, and show the corresponding improved phase space portraits. The proposed method is useful for interpolating low-sampled time series data sets for, e.g., machine learning, regression analysis, or time series prediction approaches.

The integration of advanced image analysis using artificial intelligence (AI) is pivotal for the evolution of autonomous vehicles (AVs). This article provides a thorough review of the most significant datasets and the latest state-of-the-art AI solutions employed in image analysis for AVs. Datasets such as Cityscapes, NuScenes, and CARLA form the benchmarks for training and evaluating different AI models, with unique characteristics catering to various aspects of autonomous driving. Key AI methodologies, including Convolutional Neural Networks (CNNs), Recurrent Neural Networks (RNNs), Transformer models, and Generative Adversarial Networks (GANs), are discussed. The article also presents a comparative analysis of various AI techniques in real-world scenarios, focusing on semantic image segmentation, 3D object detection, and vehicle control in virtual environments. Simultaneously, the role of multisensor datasets and simulation platforms like AirSim, TORCS, and SUMMIT in enriching the training data and testing environments for AVs is highlighted. By synthesizing information on datasets, AI solutions, and comparative performance evaluations, the article serves as a crucial resource for researchers, developers, and industry stakeholders. Offering a clear view of the current landscape and future directions in autonomous vehicle image analysis technologies.

Fractional calculus gained a lot of attention in the last couple of years. Researchers discovered that processes in various fields follow rather fractional dynamics than ordinary integer-ordered dynamics, meaning the corresponding differential equations feature non-integer valued derivatives. There are several arguments for why this is the case, one of them being that fractional derivatives’ inherit spatiotemporal memory and/or the ability to express complex naturally occurring phenomena. Another popular topic nowadays is machine learning, i.e., learning behavior and patterns from historical data. In our ever-changing world with ever-increasing amounts of data, machine learning is a powerful tool for data analysis, problem-solving, modeling, and prediction. It further provides many insights and discoveries in various scientific disciplines. As these two modern-day topics provide a lot of potential for combined approaches to describe complex dynamics, this article reviews combined approaches of fractional derivatives and machine learning from the past, puts them into context, and thus provides a list of possible combined approaches and the corresponding techniques. Note, however, that this article does not deal with neural networks, as there already is profound literature on neural networks and fractional calculus. We sorted past combined approaches from the literature into three categories, i.e., preprocessing, machine learning & fractional dynamics, and optimization. The contributions of fractional derivatives to machine learning are manifold as they provide powerful preprocessing and feature augmentation techniques, can improve physically informed machine learning, and are capable of improving hyperparameter optimization. Thus, this article serves to motivate researchers dealing with data-based problems, to be specific machine learning practitioners, to adopt new tools and enhance their existing approaches.

Plant biomass could become a new world-class "currency" because almost everything can be made of it: fuels, foods, feeds, constructing materials, furniture, etc. Currently, growing biomass for energy needs is particularly relevant in so complicated socioeconomical situation. There are important its productivity and the lowest possible ecological footprint. Can increasing crop biodiversity address these challenges? A field experiment was started at the Vytautas Magnus University Agricultural Academy in 2020-2022. Maize, hemp and faba bean were grown as single, binary and ternary crops to determine its effect on soil properties. Studies have shown that most intercrops failed to stabilize soil aggregate composition, NPK levels and pH, and enzyme urease activity. Binary maize-hemp and the ternary crops reduced the amount of the main macroelements in the soil the most because of the highest yields, which were removed from the fields. Regardless of the ecological services provided by faba beans, biomass removal leads to degradation of most soil properties and making the soil vulnerable to erosion. In the future, the cultivation of such multicrops should be investigated under conditions of more abundant fertilization or the effect of green manure should be used by increasing the number of fast- and short-growing interior plant species in the cultivation.

In this study we have investigated the effect of the addition of Nb2O5 (up to 5 mol%) on the structure and luminescent properties of ZnO-B2O3 glass doped with 0.5 mol % Eu2O3 by using of infrared (IR), Raman and photoluminescence (PL) spectroscopy. Physical properties as molar volume, oxygen packing density and glass transition temperature were determined using the results of differential thermal analyisis (DTA) and Archimedes principle for density. IR and Raman spectra revealed that niobium ions incorporate into the base zinc borate glass as NbO4 trtraherda and NbO6 octahedra. A strong red emission from the 5D0 level of Eu3+ ions was registered under near UV (392 nm) excitation using the sharp 7F0 - 5L6 transition of Eu3+. The integrated fluorescence intensity ratio R (5D0 → 7F2/5D0 → 7F1) was calculated to estimate the degree of asymmetry around the active ion, suggesting a location of Eu3+ in non-centrosymmetric sites. The higher Еu3+ luminescence emission observed in zinc borate glasses containing 1÷5 mol% Nb2O5 compared to the Nb2O5-free zinc borate glass evidences that Nb2O5 is suitable component for modification of host glass structure and improving the emission intensity.

Multi-cropping can solve the energy and GHG balance problems, but the emergence, development and productivity of such mixed crops are at risk due to increasing drought periods. For this reason, single maize crops with inter-row mellowing and weed-mulching practices were compared with faba bean, crimson and Persian clover, and alfalfa intercropped maize cultivations. Tests were performed at the Experimental Station of Vytautas Magnus University, Lithuania. Results showed that by the 30% higher energy inputs were calculated in technologies with intercropped crimson, Persian clover, and alfalfa than in monocropped maize. Single maize crops produced by the 23-40% higher biomass yields compare to clover and alfalfa intercropped maize because, due to the drought periods, intercrops weakly sprouted and developed. Lower harvests reduced the energy output by up to 38%, energy efficiency ratio - by up to 2.5 times and net energy - by up to 42%. All tested technologies were environmentally friendly and similar according to the CO2 equivalent. Long-term drought periods during vegetative season due to climate change make us think about the improvement of intercropping technologies. Sowing intercrops at the same time with maize could solve the problem of its germination but highlight the problem of abundant weed spread. Therefore, this takes us to another sphere of agrotechnologies - the effective non-chemical weed control.

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

Considering the unquestionable role of education in economic development, it has an impact at a macroeconomic level—contributing to enhancing productivity and innovation, reducing poverty and promoting social cohesion—and at a personal level—ensuring the improvement of knowledge, skills and individual capabilities and promoting social values like empowerment and equality. Notably, quality education is recognized as one of the Sustainable Development Goals (SDGs), which, jointly with other behaviors and attitudes, could impact the development of societies in other fields like health and well-being, cultural preservation, environmental sustainability and even peace and stability—all of them also listed as SDGs. However, the capacity, or not, to reach higher levels of compliance with quality in education (SDG 4) varies from country to country, according to the 2023 Sustainable Development Report results. Thus, the present study used a fuzzy set qualitative comparative analysis to assess the conditions for attaining higher levels of quality education based on the different indicators used to measure SDG 4. The analysis will allow comparisons of results among different countries and provide information about the initiatives that could be relevant to increasing quality education worldwide and for policymakers.

Highly-doped graphene samples show the conductance reduced and the shot-noise power enhanced compared to standard ballistic systems in two-dimensional electron gas. These features can be understood within a model assuming incoherent scattering of Dirac electrons between two interfaces separating the sample and the leads. Here we find, by adopting the above-mentioned model for the edge-free (Corbino) geometry and by means of the computer simulation of quantum transport, that another graphene-specific feature should be observable when the current flow through a doped disk is blocked by high magnetic field. In case the conductance drops to zero, the Fano factor approaches the value of $F\approx{}0.56$, with a very weak dependence on the disk radii ratio. The role of finite source-drain voltages and the system behavior upon tuning the electrostatic potential barrier from a rectangular to parabolic shape are also discussed.

The compound, C27H23N3 (1), crystallizes in the triclinic system of the P-1 space group. The unit cell comprises a dimer of 1, in which the monomers are linked by two complementary hydrogen bonds between N1 and H1-C1 of another molecule. The dimers form chains along the a-axis through intermolecular interactions between the N2 acceptor atoms and C17 donors from molecules in the nearest neighbouring dimer. These interactions form extended sheets of the dimers of 1, along the ab plane. The quinolinylmeth-2-yl groups of 1 lie in almost orthogonal planes and their N1/2(q) donor atoms being away from the apical amino N3 atom.

Multicropping can solve the energy and GHG balance problems, but the emergence, development and productivity of such mixed crops are at risk due to uneven distribution of precipitation. For this reason, investigations were performed at the Experimental Station of Vytautas Magnus University, Lithuania. Single maize crop was compared with Crimson/red clover, Persian clover, and alfalfa intercropped maize cultivations. Results showed that under arid conditions, the intercrops biomass was about 4 times less than under humid. Humid conditions were less suitable for maize and when growing with intercrops they produced about 3-5 t ha-1 less dried biomass, and when growing sole - about 6 t ha-1 less biomass than in arid conditions. Due to the higher yield of maize biomass in arid season, better energy indicators of the crop were obtained in arid conditions than in humid. The difference between net energy was about 122-123 MJ ha-1 in all treatments, except for the maize crop with intercropped alfalfa, where the difference was 62 MJ ha-1. All tested technologies were environmentally friendly, CO2 equivalent varied between treatments from 804 to 884 kg ha-1. Uneven distribution of precipitation during vegetative season makes us think about the improvement of intercropping technologies. Sowing intercrops at the same time with maize could improve its germination but increase the problem of weed spread.

Handedness reflects functional body and hemispheric lateralization, proving relevant to contextualize cognitive and behavioral profiles. This study aimed to determine the lateralization of the hands, feet and eyes in patients with various neurological disorders and to test the Edinburgh Handedness Inventory (EHI), a widely used handedness measure. The study design included a literature overview and a clinical study. The overview spanned the literature of the past 50 years since the EHI was developed. Three hundred seventy-four patients with immune-mediated (IM) or noIM neurological diseases and healthy subjects underwent personal and family history of handedness, stressful events and IM diseases, and EHI. The literature overview showed that handedness, which develops under the influence of genetic and acquired factors, is an indirect indicator of hemispheric lateralization; hemispheric lateralization is bidirectionally related to the immune system. In the clinical study, the EHI showed appropriate reliability and structural validity; its scores related to chronological age, onset age, and disease duration and helped distinguish patients with IM disease from other patients and healthy subjects. Therefore, handedness may change over the course of life under the influence of pathology and could predict IM neurological diseases. The EHI is an appropriate measure of handedness.

The usage of classic segmentation methods has drastically decreased recently. Implementation of convolutional neural networks and their modifications leads to significantly improved results. With the help of U-net, you can perform automatic segmentation. However, this requires significantly more hardware and software resources. The use of cloud computing now provides a wide range of possibilities, which allows processing and sharing the obtained experience and results to improve the quality of diagnosis. This article presents an approach to implementing MLOPS for automatic image segmentation using U-net technology. The approach's key feature is the developed software block that allows the creation of a dataset based on given rules. The infrastructure also supports automatically deploying the necessary environment on the cloud, particularly on DigitalOcean.

The aim of this cross-sectional study was to assess the influence of the maturity status on speed, explosive power and change of direction (COD) in 13-year-old football players. Ninety-eight male players (age: 13.1 ± 1.0 y) were divided into late, average, and early maturation groups. Physical fitness testing included the following variables: 10 and 30-meter sprint time and maximum speed in the 20-30 m segment of the 30-meter sprint test, the T-test time, countermovement jump height and horizontal distance in the triple jump. The data showed a significant effect of maturity status on performance in three parameters: in maximum speed in the 20-30 m section (p = 0,024), however, the only significant differences were found between the early-maturation group and average-maturation group (p = 0.033); in the COD (p = 0.024), where significant differences were confirmed between the late-maturation group and the average-maturation group (p = 0.033); in the unilateral triple jump distance of the dominant and non-dominant (p = 0,007 and p = 0.001, respectively) lower limb. For both limbs, significant differences between the late-maturation group and average maturation group (p = 0.005 and p = 0.013, respectively) as well as the late-maturation group and early-maturation group (p = 0.007 and p = 0.045, respectively) were proved. These results indicate that maximal speed, COD speed and unilateral lower limb reactive strength are moderated by biological age in football players aged 13 years.

2,7-bis(pyridin-4-ylethynyl)-9H-carbazole (1) was synthesized by reacting 4-ethynylpyridine hydrochloride with 2,7-dibromo-9H-carbazole. The full characterization of compound 1 is presented, and the crystal structure of its monohydrate co-crystal was determined by single-crystal XRD analysis.

Multi-cropping is becoming an increasingly popular approach in agriculture to tackle major and complex agroecosystem problems such as biodiversity and soil fertility losses, erosion and degradation, increased greenhouse gas emissions, etc. Comprehensive assessment of the impact of multi-cropping intensity on the agroecosystem is a new and still under-researched approach that provides a better understanding of the impact of the individual indicators studied on the overall functioning of the biodiversed agroecosystems. Data from a stationary field experiment with multi-cropping at the Vytautas Magnus University, Experimental Station between 2020 and 2022 were used to achieve this objective. The study included maize, hemp and faba bean as single, binary, and ternary crops. A complex assessment approach (CEI value) was used to determine the impact of these diversified crops on the agroecosystem, the interrelationships between the main indicators and the strength of their effects. It was found that the most positive effect on agroecosystem had ternary maize-hemp-faba bean crop. The effectiveness of other crops was from 2 to 35% less. The lowest one was calculated for the maize-faba bean crop.

Candidiasis is one of the global public health problems. In fluconazole resistant Candida spp. (FRCS), mutations in ergosterol biosynthesis gene 11 (ERG 11) have been commonly found. This study aimed to determine the profile of FRCS isolates and to detect mutations in part of ERG 11 gene in fluconazole resistant Candida albicans (FRCA) isolates. Study was conducted on 150 isolates of FRCS obtained from patients admitted in a tertiary care hospital, South India from September 2019 to December 2021. Candida spp. was identified by MALDI-TOF MS and fluconazole resistance was detected by VITEK 2 system. Following which a part of the ERG 11 gene of the FRCA isolates were amplified, purified, sequenced and a phylogenetic tree was constructed. Out of the 150 FRCS, the most common FRCS was C. auris followed by C. glabrata, C. krusei, C. parapsilosis, C. albicans, C. tropicalis and C. guilliermondii. Sequencing of amplicons detected a single missense mutation and 44 silent mutations. We opined that fluconazole resistance in FRCA isolates may be due to mecha-nisms other than the studied one in our region. Phylogenetic analysis of amplified sequences of 12 FRCA isolates observed three clusters and all 12 sequences showed relatedness to Malaysian 2019 isolates.

The short-lived positron-emitter carbon-11 (t1/2 = 20.4 min; b+, 99.8%) is prominent for labeling tracers for use in biomedical research with positron emission tomography (PET). Carbon-11 is produced for this purpose with a cyclotron, nowadays almost exclusively by the 14N(p,a)11C nuclear reaction, either on nitrogen containing a low concentration of oxygen (0.1–0.5%) or hydrogen (~ 5%) to produce [11C]carbon dioxide or [11C]methane, respectively. These primary radioactive products can be produced in high yields and with high molar activities. However, only [11C]carbon dioxide has some utility for directly labeling PET tracers. Primary products are required to be converted rapidly and efficiently into secondary labeling synthons to provide versatile radiochemistry for labeling diverse tracer chemotypes at molecular positions of choice. This review surveys known gas phase transformations of carbon-11 and summarizes the important roles that many of these transformations now play for producing a broad range of labeling synthons in carbon-11 chemistry.

Thrombosis after severe acute respiratory syndrome coronavirus 2 vaccination is a serious complication in patients who have a thrombophilic predisposition. In this case, a female patient with no family history of thrombophilia who had pediatric antiphospholipid syndrome (APS) developed deep vein thrombosis (DVT) when she was 6 years old; 6 months after receiving a second dose of the BNT162b2 vaccine, DVT reoccurred. The original thrombi were found in the right common iliac vein and the inferior vena cava, with concomitant left pulmonary infarction. The patient was treated with anticoagulants for 6 years after DVT onset, with subsequent treatment cessation for 5 years without recurrence. She received the BNT162b2 vaccine at 17 years of age, 1 week before a routine outpatient visit. Platelet factor 4 elevation was detected 14 days after the first vaccination, persisting for 5 months without thrombotic symptoms. Six months after the second vaccine dose, the DVT recurred and was treated with a direct oral anticoagulant. The vaccine exacerbated the patient’s APS by activating coagulation, causing thrombosis recurrence. Platelet factor 4 levels may indicate coagulation status. When patients predisposed to thrombosis are vaccinated, coagulation status and platelet activation markers should be monitored to prevent DVT development.

Two ferrocene derivatives, namely, 1,2-(tetramethylene)-ferrocene and 1,2,1’,2’-bis(tetramethylene)-ferrocene, were synthesized in a four-step reaction sequence starting from ferrocene. Friedel-Craft acylation of ferrocene with succinic anhydride gave mono- or bis(3-carboxypropinoyl)ferrocene depending on the stoichiometry of succinic anhydride. The reduction of the keto groups to methylene, followed by ring-closing using trifluoroacetic anhydride gave 1,2-(α-ketotetramethylene)-ferrocene or 1,2,1’,2’-bis(α-ketotetramethylene)ferrocene. The diastereomeric mixture of the latter diketones was separated by column chromatography, characterized by single-crystal X-ray analysis, and assigned their stereochemistry. Reduction of the keto groups to methylene under Clemmensen conditions gave homoannular mono- or bis(tetramethylene) ferrocene derivatives. The molecular structure of 1,2-(tetramethylene)-ferrocene revealed that the ipso carbon atoms of the cyclopentadienyl group are 0.023(3) Å farther away from Fe(II) compared to the remaining three carbon atoms. Both complexes exhibit lower half-wave oxidation potentials than ferrocene, possibly due to the electron-releasing effects of the tetramethylene bridges.

Attention deficit hyperactivity disorder (ADHD) is the most common childhood-onset neurodevelopmental disorder characterized by difficulty maintaining attention, impulsivity and hyperactivity. Although the cause of this disorder is still unclear, recent studies state that heredity is important in the development of ADHD. This is linked to a few comorbidities: depression, criminal behavior and anxiety. Although genetic factors play a major role in the pathogenesis of ADHD, there are also non-genetic factors, one of which would be oxidative stress (OS) that are associated with ADHD. OS is implicated in the pathogenesis of ADHD, through lower levels of antioxidant enzymes such as glutathione peroxidase (GPx), catalase (CAT), and superoxide dismutase (SOD), as well as a lower total antioxidant status (TOS) compared to control groups. Moreover, there is a close bidirectional connection between the nervous system and the intestinal microbiota, and the communication between the two systems is carried out through the gut-brain axis (GBA). A thorough review of diet, OS implications, mechanism of action, pharmacokinetics, and drug-drug interactions are reviewed here, with a special focus on treatment in adults with comorbid conditions.

The increasing emergence of multidrug resistant (MDR) pathogens, due to antibiotics misuse, translates in obstinate infections, with high morbidity and high-cost hospitalizations. To oppose these MDR superbugs, new antimicrobial options are necessary. Although both quaternary ammonium (QASs) and phosphonium salts (QPSs) possess antimicrobial effects, QPSs have been studied at lesser extent. Recently, we have successfully reported on the bacteriostatic and cytotoxic effects of a triphenyl phosphonium salt against MDR isolates of Enterococcus and Staphylococcus genus. Here, aiming at finding new antibacterial devices possibly bactericidal towards a broader spectrum of clinically relevant bacteria, responsible for severe human infections, we synthesized a water-soluble, sterically hindered quaternary phosphonium salt (BPPB). It encompasses two triphenyl phosphonium groups linked by a C12 alkyl chain, thus embodying the characteristics of molecules known as bola-amphiphiles. BPPB was characterized by ATR-FTIR, NMR and UV spectroscopy, FIA-MS (ESI), elemental analysis and potentiometric titrations. Optical and DLS analyses evidenced BPPB tendency to self-forming spherical vesicles in solution (45 nm by DLS), having a positive zeta potential (+18 mV). The antibacterial effects of BPPB were for the first time assessed against fifty clinical isolates of both Gram-positive and Gram-negative species. Excellent antibacterial effects were observed on all strains tested, involving all the most worrying species included in ESKAPE bacteria. The lowest MICs were 0.250 µg/mL, while the highest ones (32 µg/mL) were observed on MDR Gram-negative metallo-β-lactamase-producing bacteria and/or species resistant also to colistin, carbapenems, cefiderocol, so that intractable with current available antibiotics. Moreover, when administered to HepG2 human hepatic and Cos-7 monkey kidney cell lines, BPPB showed selectivity indices > 10 for all Gram-positive isolated and for clinically relevant Gram-negative superbugs such as those of E. coli species, thus being very promising to be clinically developed.

Background: Ovarian cancer is the leading cause of death from gynecological malignancies with serous carcinoma being the most common histopathologic subtype. Epithelial-Mesenchymal Transition (EMT) correlates with an increased metastatic potential, whereas the transcription factor SOX11 is overexpressed in diverse malignancies. Methods: In the present study, we aim to evaluate the potential role of the immunohistochemical expression of SOX11 in 30 serous ovarian carcinomas in association with E-cadherin and Vimentin expression as well as with patients’ clinicopathological data. Results: Most of the examined cases showed concurrent expression of E-cadherin and Vimentin, whereas SOX11 was expressed in a minority of the cases (26,7%). Interestingly, the positive cases had more frequently a metastatic disease at the time of diagnosis compared to the negative cases (p=0.09), an association, however, of marginal significance. Moreover, there was a negative correlation between E-Cadherin and SOX11 expression (p=0,0077) and a positive correlation between Vimentin and SOX11 expression (p=0,0130). Conclusions: The present work, for the first time, provides preliminary evidence SOX11 overexpression alongside E-cadherin loss in the promotion of EMT in serous ovarian cancer, thereby endorsing tumor metastasis.

Land cover mapping, essential for understanding global land use patterns, relies on satellite imagery for monitoring changes, assessing ecosystem health, and supporting conservation ef- forts. However, significant challenges remain in managing large, complex satellite imagery datasets, acquiring specialized datasets due to high costs and labor intensity, and a lack of comparative studies for optimal deep learning model selection. Additionally, a scarcity of aerial datasets specifically tailored for agricultural areas exists. This study addresses these gaps by presenting a method for semantic segmentations of land covers in agricultural areas using satellite images and deep learning models with pre-trained backbones. We introduce an efficient methodology for preparing semantic segmentation datasets and contribute the "Land Cover Aerial Imagery" (LICAID) dataset for semantic segmentation. The study focuses on the Franciacorta area, Lombardy Region, leveraging the rich diversity of the dataset to effectively train and evaluate the models. We conduct a comparative study, employing cutting-edge deep learning-based segmentation models (U-Net, SegNet, DeepLabV3) with various pre-trained backbones (ResNet, Inception, DenseNet, EfficientNet) on our dataset acquired from Google Earth Pro. Through meticulous data acquisition, preprocessing, model selection, and evaluation, we demonstrate the effectiveness of these techniques in accurately delineating land cover classes. Integrating pre-trained feature extraction networks significantly improves performance across various metrics. Additionally, addressing challenges such as data availability, computational resources, and model interpret-ability is essential for advancing the field of remote sensing and supporting sustainable environmental stewardship worldwide.

The accurate state of health (SOH) estimation of lithium-ion batteries (LIBs) during operation is crucial to ensure optimal performance, prolonging battery life and preventing unexpected failure or safety hazards. This work presents a storage and performance optimised deep learning approach to predict the capacity based SOH of LIBs using raw sensor data from partial charging curves under constant current condition. The proposed model is based on a combination of a 1-dimensional convolutional and long-short term memory neural network and processes time, voltage and incremental capacity of partial charging curves as time series. The model is cross-validated on different aging scenarios reaching an overall MAE = 0.418% and RMSE = 0.531%, promising an accurate SOH estimation of LIBs under varying usage and environmental conditions in a real world application.

In order to investigate the coordination chemistry of O-alkyl N-aryl thiocarbamate ligands, BiI3 has been reacted with two equivalents of MeOC(=S)N(H)Ph in MeCN solution to afford the dinuclear title compound complexes [{I2Bi(μ2-I)2BiI2}{1-MeOC(=S)N(H)Ph}4] 1. Compound 1 has been characterized by IR, UV and NMR spectroscopy, the dinuclear framework has be ascertained by a single-crystal X-ray diffraction study performed at 100 K.

Photophysical properties of a series of bis(arylydene)cycloalkanone dyes with various donor substituentns are studied by quantum chemistry. Their capacity for luminescence and nonradiative relaxation through trans-cis isomerization is related to their structure, in particular, to the donor capacity of the substituents and the degree of conjugation due to the central cycloalkanone moiety. It is shown that cyclohexanone central moiety introduces distortions and disrupts the conjugation, thus leading to a nonmonotonic change in their properties. The increasing donor capacity of the substituents causes increase in the HOMO energy (raise of the oxidation potential) and decrease in the HOMO-LUMO gap, which results in the red shift of the absorption spectra. The ability of the excited dye to relax through fluorescence or through trans-cis isomerization is governed by the height of the barrier between the Franck–Condon and S1-S0 conical intersection regions on the potential energy surface of the lowest π-π* excited state. This barrier also correlates with the donor capacity of the substituents and the degree of conjugation between the central and donor moieties. The calculated fluorescence and trans-cis isomerization rates are in good agreement with the observed fluorescence quantum yields.

Background: Autism spectrum disorder (ASD) is a persistent neurodevelopment disorder frequently co-occurring with Attention-Deficit/Hyperactivity Disorder (ADHD) and behavior-related disorders. While behavioral therapy is the first-line option to manage ASD core symptoms, pharmacological therapy is sometimes needed to treat acute problems, such as agitation and aggressive behaviors. Recent guidelines recommend neuroleptics to reduce psychomotor agitation in people with ASD. However, since children with ASD are often drug-resistant, alternative treatments are often justified. Reports from literature showed that intra-venous valproate (IV-VPA) can be effective in reducing agitation in psychiatric patients, with lower frequency of adverse events compared to convention-al treatments. However, since findings are occasionally inconsistent, IV-VPA is not an approved option in clinical psychiatry. We aim at improving the knowledge on the IV-VPA treatment option in emergency psychiatry in the pediatric age. Methods: We report the case of a 11-year-old boy suffering from a complex neurodevelopmental condition, who experienced a psychotic episode with severe aggressive and disruptive behaviors, successfully treated with IV-VPA. Besides, we conducted an up-dated literature review on this topic. Conclusion: In our case, first-line therapies proved to be ineffective. On the contrary, IV-VPA led to a safe and prompt clinical success, in line with other reports. Based on our literature review, IV-VPA can be highly effective and can reduce the risk of adverse events that frequently occur with the use of high-dose standard medications in emergency psychiatry.

(1) Background Diabetic Retinopathy (DR) is the primary cause of poor vision in young adults. Screening for DR is important but many patients do not attend; (2) Methods: We validated an algorithm for predicting DR and its progression by conducting a retrospective study of 11 children in a population of 120,389 T2DM (3) Results: By applying the algorithm to the population showed an AUC of 0.93 (95% CI, 0.92–0.94) for any-DR and 0.90 (95% CI, 0.89–0.91) for referable-DR(4) Conclusions: The algorithm is useful for predicting patients who could develop referable forms of DR and also for any-DR. This would allow a personalized screening plan to be drawn up for each patient.

Oligonucleotide conjugates with boron clusters have found applications in different fields of molecular biology, biotechnology, and biomedicine as potential agents for boron neutron capture therapy, siRNA components, and antisense agents. Particularly, closo-dodecaborate anion represents a high-boron containing residue with remarkable chemical stability and low toxicity, suitable for the engineering of different constructs for biomedicine and molecular biology. In the present work, we synthesized novel oligonucleotide conjugates of closo-dodecaborate attached to the 5'-, 3'-, or both terminal positions of DNA, RNA, 2'-O-Me RNA, and 2'-F-Py RNA oligomers. For their synthesis, we employed click reaction with the azido derivative of closo-dodecaborate. The key physicochemical characteristics of the conjugates have been investigated using high-performance liquid chromatography, gel electrophoresis, UV thermal melting, and circular dichroism spectroscopy. Incorporation of closo-dodecaborate residues at the 3'-end of all oligomers stabilized their complementary complexes, while analogous 5'-modification decreased duplex stability. Two boron clusters attached to the opposite ends of the oligomer only slightly influence the stability of complementary complexes of RNA oligonucleotide and its 2'-O-methyl and 2'-fluoro analogs. On the contrary, the same modification of DNA oligonucleotides significantly destabilized DNA/DNA duplex but gave a strong stabilization of the duplex with RNA target. According to CD spectroscopy results, two terminal closo-dodecaborate residues cause a prominent structural rearrangement of complementary complexes with a substantial shift from B-form to the A-form of the double helix. The revealed changes of key characteristics of oligonucleotides caused by incorporation of terminal boron clusters, such as the increase of hydrophobicity, change of duplex stability, and prominent structural changes for DNA conjugates, should be taken into account for the development of antisense oligonucleotides, siRNAs, or aptamers bearing boron clusters. These features may also be used for engineering of developing NA constructs with pre-defined properties.

Business-to-business (B2B) manufacturing companies are increasingly confronted with transformative trends such as sustainability, digitalization, and servitization. These trends are changing how product portfolios are developed, and value contributions are assessed, and therefore have disruptive potential. Dealing with these disruptive factors in Product Portfolio Management (PPM) is a largely unexplored topic. This study presents an empirical-qualitative exploration that contributes significantly to the field. The aim is to clarify the extent to which disruptive factors influence the evaluation and shaping of the product portfolio in B2B manufacturing companies. The Gioia method was used to evaluate 21 semi-structured interviews with experts from leading B2B manufacturing companies. Eight overarching challenges in PPM resulting from the disruptive factors were identified. Based on the eight overarching challenges and their associated causal relationships, two aggregated dimensions of action were derived: (1) increasing speed and flexibility by using generative artificial intelligence (AI) in a defined PPM process and (2) adjusting the product portfolio evaluation to consider various strategic drivers. These two dimensions of action call for future research to overcome the disruptive factors in PPM.

Background and aims: Despite recent advances in advanced prostate cancer treatments, there are no clinically useful biomarkers or treatments for men with such cancers. Targeted therapies have shown promise, but there remain fewer actionable targets in prostate cancer than in other cancers. This work aims to characterize BRD9, currently understudied in prostate cancer, and investigate its co-expression with other genes to assess its potential as a biomarker and therapeutic target in human prostate cancer. Materials and methods: Omics data from a total of 2053 prostate cancer patients across 11 independent datasets were accessed via Cancertool and cBioPortal. mRNA expression and co-expression, mutations, amplifications, and deletions were assessed with respect to key clinical parameters including survival, Gleason grade, stage, progression and treatment. Network and pathway analysis was carried out using Genemania, and heatmaps were constructed using Morpheus. Results: BRD9 is overexpressed in prostate cancer patients, especially those with metastatic disease. BRD9 expression did not differ in patients treated with second generation antiandrogens versus those who were not. BRD9 is co-expressed with many genes in the SWI/SNF and BET complexes, as well as those in common signaling pathways in prostate cancer. Summary and conclusions: BRD9 has potential as a diagnostic and prognostic biomarker in prostate cancer. BRD9 also shows promise as a therapeutic target, particularly in advanced prostate cancer, and as a co-target alongside other genes in the SWI/SNF and BET complexes, and those in common prostate cancer signalling pathways. These promising results highlight the need for wider experimental inhibition and co-targeted inhibition of BRD9 in vitro and in vivo, to build on the limited inhibition data available.

In this paper, we redefine the boundaries of blood cell classification, expanding from 5 to 11 distinct blood cell types using the challenging 11-class PBC dataset. This shift enables a deeper understanding of blood cell diversity, overcoming previous limitations in medical image analysis. Our approach combines state-of-the-art deep learning techniques, including pre-trained ConvNets, ViTb16 models, and custom CNN architectures. We employ transfer learning, fine-tuning, and ensemble strategies, such as CBAM and Averaging ensembles, to achieve unprecedented accuracy and interpretability. Our fully fine-tuned EfficientNetV2 B0 model sets a new standard, with a macro-average precision, recall, and F1-score of 91%, 90%, and 90%, respectively, and an average accuracy of 93%. This breakthrough underscores the transformative potential of 11-class blood cell classification for more precise medical diagnoses. Moreover, our groundbreaking "Naturalize" augmentation technique produces remarkable results. The 2K-PBC dataset generated with "Naturalize" boasts a macro-average precision, recall, and F1-score of 97%, along with an average accuracy of 96% when leveraging the fully fine-tuned EfficientNetV2 B0 model. This innovation not only elevates classification performance but also addresses data scarcity and bias in medical deep learning. Our research marks a paradigm shift in blood cell classification, enabling more nuanced and insightful medical analyses. The "Naturalize" technique’s impact extends beyond blood cell classification, emphasizing the vital role of diverse and comprehensive datasets in advancing healthcare applications through deep learning.

The 11 system in iron-based superconducting family has become one of the most extensively studied materials in the research of high-temperature superconductivity due to their simple structure and rich physical properties. However, the research on 11 iron-based superconductors faces numerous obstacles, mainly stemming from the challenges associated with producing high-quality single crystals. Since the discovery of FeSe superconductivity in 2008, researchers have made significant progress in crystal growth, overcoming the hurdles that initially impeded their studies. Consequently, they have successfully established the complete phase diagrams of 11 iron-based superconductors, including FeSe1-xTex, FeSe1-xSx and FeTe1-xSx. In this paper, we aim to provide a comprehensive summary of the preparation methods employed for 11 iron-based single crystals over the past decade. Specifically, we will focus on hydrothermal, chemical vapor transport (CVT), self-flux, and annealing methods. Additionally, we will discuss the quality, size, and superconductivity properties exhibited by single crystals obtained through different preparation methods. By exploring these aspects, we can gain a better understanding of the advantages and limitations associated with each technique.

Salmonella enterica serovar Newport bacteriophage 7-11 shares 41 homologous ORFs with Escherichia coli phage phiEco32 and both phages encode a protein similar to bacterial RNA polymerase promoter specificity  subunit. Here, we investigated the temporal pattern of 7-11 gene expression during the infection and compared it to the previously determined transcription strategy of phiEco32. Using primer extension and in vitro transcription assays we identified eight promoters recognized by host RNA polymerase holoenzyme containing 7-11  subunit SaPh711_gp47. These promoters are characterized by a bipartite consensus GTAAtg-(16)-aCTA and are located upstream of late phage genes. While dissimilar from single-element middle and late promoters of phiEco32 recognized by holoenzyme formed by the phi32_gp36  factor, the 7-11 late promoters are located at genome positions similar to those of phiEco32 middle and late promoters. Two early 7-11 promoters are recognized by RNA polymerase holoenzyme containing host primary σ70 factor. Unlike the case of phiEco32, no shut off of σ70-dependent transcription is observed during 7-11 infection and there are no middle promoters. These differences can be explained by the fact that phage 7-11 does not encode a homologue of phi32_gp79, an inhibitor of host and early phage transcription and an activator of transcription by the phi32_gp36-holoenzyme.

Currently, obesity is a critical global public health burden. Numerous studies have demonstrated the regulation of the pathogenesis of obesity and metabolic abnormalities by the gut microbiota and microbial factors; however, their involvement in the various degrees of obesity is not yet understood well. Previously, obesity has been shown to be associated with decreased levels of vitamin B12. Considering exclusive microbial production of vitamin B12, we hypothesised that a decrease in cobalamin levels in obese individuals may be at least partially caused by its depleted production in the intestinal tract by the commensal microbiota. In the present study, our aim was to estimate the abundance of enzymes and metabolic pathways for vitamin B12 synthesis in the gut microbiota of mouse models of alimentary and genetically determined obesity, to evaluate the contribution of the obesogenic microbiome to vitamin B12 synthesis in the gut. We have defined a significantly lower representation of enzymes and metabolic pathways for vitamin B12 biosynthesis in obese mice compared to non-obese mice, wherein enzyme depletion was more pronounced in lepr(-/-) (db/db) mice, which developed severe obesity. The representation of enzymes involved in cobalamin synthesis is strongly correlated with representation of several microbes in high-fat diet fed mice, whereas there were almost no correlations in db/db mice. Therefore, the degree of obesity and the composition of the correspondent microbiota are the main contributors to the representation of genes and pathways for cobalamin biosynthesis in the mouse gut.

Schizophrenia is a complex mental disorder influenced by genetic and environmental factors, including diet. Oxidative stress and inflammation play a crucial role in the pathophysiology of schizophrenia. Nutritional deficiencies, such as lack of omega-3 fatty acids, vitamin D, and B vitamins, during prenatal and postnatal periods can nega-tively impact neurodevelopment and increase the risk of schizophrenia. Patients with schizophrenia show imbalances in antioxidant enzymes such as: glutathione peroxidase (GPx), superoxide dismutase (SOD), catalase (CAT) and reduced levels of antioxidants (vitamin E, vitamin C), leading to increased oxidative stress markers such as malondialdehyde (MDA). Cytokine-mediated inflammation, microglial activation, and gut dysbiosis are associated with schizophrenia onset and symptom severity. There is no clear and universally accepted diet for the treatment of schizophrenia, which is considered the most popular. However, various diets and nutritional methods are being researched and applied to alleviate the symptoms of schizophrenia and improve the general health of patients, including the mediterranean diet, ketogenic diet, gluten-free diet and DASH diet. A healthy diet rich in anti-inflammatory and antioxidant nutrients can help manage schizophrenia by reducing oxidative stress, preventing complications, and improving quality of life. Omega-3 fatty acids, vitamin D and B vitamins are par-ticularly important for brain development and function. In this review we will focus on the influence of diet on schizophrenia. Additional research is needed to develop per-sonalized dietary recommendations for patients with schizophrenia.

To better understand anogenital warts (AGW) natural history and dynamic of HPV6/11 infection in regional hairs, 32 newly diagnosed AGW male patients and 32 age-matched healthy controls were closely followed. During enrollment and six follow-up visits (every 2.6 months) 43 AGW tissue and 1,232 anogenital and eyebrow hair samples were collected. This represents the closest longitudinal monitoring of AGW patients to date. Patients were treated according to standard-of-care. HPV6/11 prevalence was 19.9% in patients’ hair samples (HPV6 B1 in 87.5%) and 0% in controls. The highest HPV6/11 prevalence was found in pubic hairs (29.0%) and lowest in eyebrows (7.1%). Odds for HPV6/11-positive hairs increased with smoking, shaving anogenital region and age. A close association between HPV6/11 presence in hairs and clinically visible AGW was observed. The proportion of patients with visible AGW and HPV6/11-positive hairs declined during follow-up with similar trends. No particular HPV6/11 variant was linked with increased AGW recurrence, but sublineage HPV6 B1 showed significantly higher clearance from hairs. Despite treatment, 78.1% and 62.5% of AGW patients experienced one and two/more post-initial AGW episodes, respectively. Patients having HPV6/11-positive hairs or visible AGW at preceding visit demonstrated substantially higher odds for presenting with visible AGW in subsequent visit.

The purpose of this paper is to explore the implementation of Retrieval-Augmented Gen- 14 eration (RAG) technology with open-source Large Language Models (LLMs). For this purpose, a 15 web-based application named PaSSER that integrates RAG with three models - Mistral:7b, 16 Llama2:7b: Orca2:7b, is developed. In its development various technologies are used, including 17 Blockchain for managing and storing assessment results of built-in testing modules. PaSSER em- 18 ploys a set of evaluation metrics for LLMs’ performance - METEOR, ROUGE, BLEU, Perplexity, 19 Cosine similarity, Pearson correlation, and F1 score. The specialized knowledge base is in the smart 20 agriculture domain. As an illustration, the paper presents results and analysis of two tests. First one 21 is assessing the performance of LLMs across different hardware configurations, the other is deter- 22 mining the model that delivers most accurate and contextually relevant responses within the RAG. 23 The paper also discusses the integration of blockchain technology with LLMs to manage and store 24 assessment results within a blockchain environment. The tests revealed that Mistral:7b demon- 25 strates the best results across most of the evaluated metrics. The discussion section comments on 26 technical and hardware considerations that affect the performance of LLMs. Future development 27 will focus in leveraging new larger pre-trained open-source LLMs, exploring different finetuning 28 approaches, and further integration with Blockchain and IPFS.

The Sustainable Development Goals (SDGs) represent a central framework to guide sustainable urban development (2030 Agenda). However, it is not clear how and where SDG 11 (Sustainable Cities and Communities) is being implemented, and how such implementation might be improved. We investigated this subject by analyzing United Nations (UN) SDG Good Practices data from 2018 to 2021. We applied five criteria to the 336 SDG 11 responses: (1) geography; (2) actors; (3) progress toward targets; (4) areas of implementation; and (5) scale of action. Overall, 86 of the 193 countries that adopted the 2030 Agenda submitted at least one SDG 11 good practice. 33 countries contributed 73.8% of the total, and most developing countries did not make submissions. A very small number of responses (between 2.6 and 9.1%) addressed equity-related targets. Good practices from developed countries were usually more technology-based and system-forming; developing countries typically focused on issues of day-to-day concern. Overall, this analysis points to the need for better and more systematic reporting on SDG 11 implementation, a more active public sector role in SDG implementation and reporting, more focus on dimensions related to social equity, and better formulation of urban sustainability targets and indicators in the future.

Understanding speech in noise is particularly difficult for individuals occupationally exposed to noise due to a to a mix between noise-induced auditory lesions and energetic masking of speech signal. For years, the monitoring of conventional audiometric thresholds has been the usual way to check and preserve the auditory function. But the highlighting of supra-threshold deficits, notably speech in noise understanding difficulties, has pointed out the need for new monitoring tools. The present study aims to identify the most important variables that predict speech in noise under-standing in order to suggest a new way of regular monitoring. Physiological (distortion products of otoacoustic emissions, electrocochleography) and behavioral (amplitude and frequency modula-tion detection thresholds, conventional and extended high frequency audiometric thresholds) variables were collected in a population of individuals presenting a relative homogeneous occu-pational noise exposure. Those variables were used as predictors in a statistical model (random forest) to predict scores of three different speech in noise tests and a self-report of speech in noise ability. The extended high frequency threshold appears to be the best predictor and therefore an interesting candidate for a new way of monitoring noise exposed professionals.

The environmental Kuznets curve (EKC) hypothesis posits an inverted U-shaped relationship between economic growth and environmental degradation. However, there is no consensus regarding the EKC hypothesis among countries and regions of different income groups. In this study, we analyze the EKC hypothesis for 158 countries and 44 regions from 1990 to 2020, categorizing them into different income groups based on the World Bank's income classification (low, lower-middle, upper-middle, and high-income countries). Our findings reveal mixed patterns in the EKC across different income levels, highlighting the heterogeneous relationship between economic growth and carbon emissions and showing differentiated patterns among different income levels. While a rise in income for high-income countries should be reflected in a shift toward fewer carbon emissions, for lower-income countries, growth is still associated with rising emissions. This underscores the urgent need for policy interventions that decouple economic development from environmental degradation. A balanced approach to economic growth, which prioritizes carbon neutrality across all stages of development, by tailoring environmental and economic strategies to address CO2 emissions effectively, should be adopted, recognizing the different developmental stages and income levels of countries and regions.

Chronic graft-versus-host disease (cGvHD) occurs in 20-50% of recipients following allogeneic haematopoietic stem cell transplantation (allo-HSCT). Corticosteroids (CS) remain the first line treatment but have suboptimal efficacy and carry the risk of long-term side effects. New agents with a better safety profile and higher efficacy, ideally combining immunomodulatory and antifibrotic properties, are urgently needed. From 2016 to 2020, we conducted a phase 2 clinical trial with ATO in chronic GvHD (ClinicalTrials.gov ID NCT02966301 - GMED16-001). This study aimed to evaluate the efficacy and safety of a first-line combination of arsenic trioxide (ATO) and CS in adult patients with cGvHD who require systemic therapy after a first allo-HSCT for a haematological disease. In this prospective, national, multicenter, single-arm, open-label phase II study, conducted in 5 university hospital centers in France, ATO was initiated within 10 days of starting CS at 1 mg/kg/day. Patients received 11 infusions of ATO per 4-week cycle, at a dose of 0.15 mg/kg per infusion. Patients received 1 or 2 cycles of treatment depending on the clinical response and the assessment of the treating physician. The results were published in July 2022 in a paper entitled "High Response Rate and Corticosteroid Sparing with ATO-Based First-Line Therapy in Chronic Graft-versus-Host Disease after Allogeneic Hematopoietic Stem Cell Transplantation". The GMED16-001 study demonstrated convincing efficacy and safety characteristics of the intravenous drug (Trisenox^®/Arscimed^®): the first-line use of ATO in addition to corticosteroids was associated with a high clinical response rate and correlated with rapid corticosteroid (CS) sparing in moderate to severe cGvHD after allo-HSCT. We performed a post-hoc analysis of the data to determine the best schedule for treating cGvHD patients with ATO. Our post-hoc analysis leads us to the conclusion that two cycles of ATO, at 0.15 mg/kg/day, 5 days per week for 4 weeks each, separated by a 4-week therapy-free interval, appears to be the most promising treatment schedule.

The present article describes the synthesis of an isonicotinate-derived meso-arylporphyrin, that has been fully characterized by spectroscopic methods (including fluorescence spectroscopy), as well as by elemental analysis and by HR-MS. The structure of a n-hexane monosolvate has been determined by single crystal X-ray diffraction analysis. The radical scavenging activity of this new porphyrin against the 2,2-diphenyl-1-picrylhydrazyl (DDPH) radical has been measured. Its antifungal activity against three yeast strains (C. albicans ATCC 90028, C. glabrata ATCC 64677 and C. tropicalis ATCC 64677) has been tested, using the disk diffusion and the microdilution methods. Whereas the measured antioxidant activity was low, the porphyrin showed moderate but encouraging antifungal activity. Finally, a study of its effect on the germination of lentil seeds revealed interesting allelopathic properties.

Assembly theory provides a promising framework to explain the complexity of systems such as molecular structures and the origins of life, with broad applicability across various disciplines. In this study, we explore and consolidate different aspects of assembly theory by introducing a simplified toy model to simulate the autocatalytic formation of complex structures. This model abstracts the molecular formation process, focusing on the probabilistic control of catalysis rather than the intricate interactions found in organic chemistry. We establish a connection between probabilistic catalysis events and key principles of assembly theory, particularly the probability of a possible construction path in the formation of a complex object, and examine how the assembly of complex objects is impacted by the presence of autocatalysis. Our findings suggest that autocatalysis tends to favor longer consecutive construction sequences in environments with low catalysis probability, while this bias diminishes in environments with higher catalysis probabilities, highlighting the significant influence of environmental factors on the assembly of complex structures.

Inflammasomes are multiprotein complexes that activate inflammatory responses by inducing pyroptosis and secretion of pro-inflammatory cytokines. Along with many previous studies on inflammatory responses and diseases induced by canonical inflammasomes, an increasing number of studies have demonstrated that non-canonical inflammasomes, such as mouse caspase-11 and human caspase-4 inflammasomes, are emerging key players in inflammatory responses and various diseases. Flavonoids are natural bioactive compounds found in plants, fruits, vegetables, and teas and have pharmacological properties in a wide range of human diseases. Many studies have successfully demonstrated that flavonoids play an anti-inflammatory role and ameliorate many inflammatory diseases by inhibiting canonical inflammasomes. Others have demonstrated the anti-inflammatory roles of flavonoids in inflammatory responses and various diseases, with a new mechanism by which flavonoids inhibit non-canonical inflammasomes. This review discusses recent studies that have investigated the anti-inflammatory roles and pharmacological properties of flavonoids in inflammatory responses and diseases induced by non-canonical inflammasomes and further provides insight into developing flavonoid-based therapeutics as potential nutraceuticals against human inflammatory diseases.

Episcopic imaging using techniques such as High Resolution Episcopic Microscopy (HREM) and its variants, allows biological samples to be visualized in three dimensions over a large field of view. Quantitative analysis of episcopic image data is undertaken using a range of methods. In this systematic review, we look at trends in quantitative analysis of episcopic images and discuss avenues for further research. Papers published between 2011 and 2022 were analyzed for details about quantitative analysis approaches, methods of image annotation and choice of image processing software. It is shown that quantitative processing is becoming more common in episcopic microscopy and that manual annotation is the predominant method of image analysis. Our meta-analysis highlights where tools and methods require further development in this field, and we discuss what this means for the future of quantitative episcopic imaging, as well as how annotation and quantification may be automated and standardized across the field.

After a long limbo, RNA has gained its credibility as a druggable target, fully earning its de-served role in the next-generation area of pharmaceutical R&D. We have recently probed the Trans-Activation Response element (TAR), a RNA stem–bulge–loop domain of the HIV-1 genome with bis-3-chloropiperidines (B-CePs), and revealed the compounds unique behavior in stabiliz-ing TAR structure, thus impairing in vitro the chaperone activity of the HIV-1 nucleocapsid (NC) protein. Seeking to elucidate the determinants of B-CePs inhibition, we have further characterized here their effects on the target TAR and its NC recognition, while developing quantitative analyti-cal approaches for the study of multicomponent RNA-based interactions.

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a‒c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2); m-, R = Me (3c-Zr2) were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

The study of different forms of preconditioners for solving a system of nonlinear equations, by using Newton’s method, is presented. The preconditioners provide numerical stability and rapid convergence with reasonable computation cost, whenever chosen accurately. Different families of iterative methods can be constructed by using a different kind of preconditioners. The multi-step iterative method consists of a base method and multi-step part. The convergence order of base method is quadratic and each multi-step add an additive factor of one in the previously achieved convergence order. Hence the convergence of order of an m-step iterative method is m + 1. Numerical simulations confirm the claimed convergence order by calculating the computational order of convergence. Finally, the numerical results clearly show the benefit of preconditioning for solving system of nonlinear equations.

The physics of Hubble's law, motivated by the anomalous acceleration of Pioneer 10/11, suggests that the Hubble constant corresponds to a gravitational field of the Universe. The Hubble constant inferred from Pioneer 10/11 data is $\sim 69$ km/s/Mpc. The anomalous acceleration of Pioneer 10/11 can be interpreted as an observational evidence for Mach's principle. The redshift is an apparent value. Its intrinsic value has a limit resulting to $v

Word Sense Disambiguation (WSD) stands as a persistent challenge within the Natural Language Processing (NLP) community. While various NLP packages exist, the Lesk algorithm in the NLTK library, a widely recognized tool, demonstrates suboptimal accuracy. Conversely, the application of deep neural networks offers heightened classification precision, yet their practical utility is constrained by demanding memory requirements. This research paper introduces an innovative method addressing WSD challenges by optimizing memory usage without compromising state-of-the-art accuracy. The presented methodology facilitates the development of WSD system that seamlessly integrates into NLP tasks, resembling the functionality offered by the NLTK library. Furthermore, this paper advocates treating the BERT language model as a gold standard, proposing modifications to manually annotated datasets and semantic dictionaries such as WordNet to enhance WSD accuracy. The empirical validation through a series of experiments establishes the effectiveness of the proposed method, achieving state-of-the-art performance across multiple WSD datasets. This contribution represents advancement in mitigating the challenges associated with WSD, offering a practical solution for integration into NLP applications.

Multi-stakeholder participation processes in watershed management face challenges due to limited monitoring and baseline data, resulting in a lack of awareness among stakeholders about the current state of the watershed. This knowledge gap often leads to conflicts of interest, where the broader impacts of individual decisions are overlooked. To overcome these limitations, this paper explores the design and implementation of a Serious Game (SG) aimed at co-producing a watershed management plan at the basin scale within the specific context of the Campoalegre River basin in Colombia. By providing an interactive platform, the SG facilitates collaboration between local actors, who may be unfamiliar with existing watershed plans, and decision-makers. The goal is to create a participatory space where stakeholders can comprehend the watershed management plan structure and prioritize actions based on various climatic, social, and economic conditions. Following the application of the SGs, stakeholders demonstrated an improved understanding of the basin, fostering increased participation, open debate, and the proposal of actions. These outcomes serve as valuable inputs for the implementation of water management planning policies, showcasing the potential of SGs in bridging knowledge gaps, and fostering effective multi-stakeholder engagement.

We explore the possibility of using the external regions of galaxy clusters to measure their mass accretion rate (MAR). The main goal is to provide a method to observationally investigate the growth of structures on the nonlinear scales of galaxy clusters. We derive the MAR by using the mass profile beyond the splashback radius, evaluating the mass of a spherical shell and the time it takes to fall in. The infall velocity of the shell is extracted from N-body simulations. The average MAR returned by our prescription in the redshift range z=[0, 2] is within 20-40% of the average MAR derived from the merger trees of dark matter haloes in the reference N-body simulations. Our result suggests that the external regions of galaxy clusters can be used to measure the mean MAR of a sample of clusters.

The kinase pathway plays a crucial role in blood vessel function. Particular attention is paid to VEGFR-type 2 angiogenesis and vascular morphogenesis as the tyrosin kinase pathway is preferentially activated. In silico studies were performed on several peptides that affect VEGFR2 in both stimulating and inhibitory ways. This investigation aims to examine the molecular properties of VEGFR2, a molecule primarily involved in the processes of vasculogenesis and angiogenesis. These relationships were defined by the interactions between vascular endothelial growth factor receptor 2 (VEGFR2) and the structural features of the systems. The chemical space of the inhibitory peptides and stimulators was described using topological and energetic properties. Furthermore, chimeric models of stimulating and inhibitory proteins (for VEGFR2) were computed using the protein system structures. The interaction between the chimeric proteins and VEGFR was computed. The chemical space was further characterized using complex manifolds and high-dimensional data visualization. The results show that a slightly similar chemical area is shared by VEGFR2 and is shared by stimulating and inhibitory proteins. On the other hand, the stimulator peptides and the inhibitors have distinct chemical spaces.

Among phosphorylated derivatives, phosphinates occupy a prominent place due to their ability to be bioisosteres of phosphates and carboxylates. These properties imply the necessity to develop efficient methodologies leading to phosphinate scaffolds. For the past years our team have explored the nucleophilic potential of silylated phosphonite towards various electrophiles. In this paper, we propose to extend our study over other electrophiles. We describe here the implementation of a cascade reaction between (trimethylsilyl)imidates and hypophosphorous acid mediated by a Lewis acid allowing the synthesis of aminomethylenebisphosphinate derivatives.

A major health threat for children in the 21st century is physical inactivity in conjunction with the elevated prevalence of obesity. In Malaysia, low physical activity among children is a major concern. The objective of the study was to analyze the day to day variation of step count in a sample of obese children using the activPAL^TM monitor. This was a cross sectional study conducted in Kuala Terengganu, Terengganu. The sample compromised 41 boys and 24 girls between the ages of 9-11 years. Number of steps was objectively measured using an activPAL^TM accelerometer over a period of 4-7 days and had their height and weight measured. Mean step count from this sample of obese children was 8861 ± 3157steps. Steps per day were significantly higher for boys compared to girls (p=0.034). Obese children took significantly more steps at weekdays than on weekends (p=0.001). Steps/hour were significantly higher in weekday compared to weekend between 0600 to 0700 (p<0.001), 0700 to 0800 (p<0.001), 0800 to 0900 am (p<0.001), 0900 to 1000 (p=0.032), 1000 to 1100 (p=0.046), 1100 to 1200 (p<0.001), 1300 to 1400 (p=0.002), 1400 to 1500 (p<0.001), 1800 to 1900 (p=0.026) and 2000 to 2100 (p=0.019). Detailed daily patterns of physical activity are required to fully understand the differences across days that help future interventions to target those falling short particularly during weekend.

In this study, we present a novel approach to estimate the Hurst exponent of time series data using a variety of machine learning algorithms. The Hurst exponent is a crucial parameter in characterizing long-range dependence in time series, and traditional methods such as Rescaled Range (R/S) analysis and Detrended Fluctuation Analysis (DFA) have been widely used for its estimation. However, these methods have certain limitations, which we sought to address by modifying the R/S approach to distinguish between fractional Lévy and fractional Brownian motion, and by demonstrating the inadequacy of DFA and similar methods for data that resembles fractional Lévy motion. This inspired us to utilize machine learning techniques to improve the estimation process. In an unprecedented step, we train various machine learning models, including LightGBM, MLP, and AdaBoost, on synthetic data generated from random walks, namely fractional Brownian motion and fractional Lévy motion, where the ground truth Hurst exponent is known. Meaning that we can initialize and create these stochastic processes with a scaling Hurst/scaling exponent which, is then used as the ground truth for training. Furthermore, we perform the continuous estimation of the scaling exponent directly from the time series, without resorting to the calculation of the power spectrum or other sophisticated preprocessing steps, as done in past approaches. Our experiments reveal that the machine learning-based estimators outperform traditional R/S analysis and DFA methods in estimating the Hurst exponent, particularly for data akin to fractional Lévy motion. Validating our approach on real-world financial data, we observe a divergence between the estimated Hurst/scaling exponents and results reported in the literature. Nevertheless, the confirmation provided by known ground truths reinforces the superiority of our approach in terms of accuracy. This work highlights the potential of machine learning algorithms for accurately estimating the Hurst exponent, paving new paths for time series analysis. By marrying traditional finance methods with the capabilities of machine learning, our study provides a novel contribution towards the future of time series data analysis.

The organic extract of the Caribbean sponge Smenospongia aurea has been shown to contain an array of novel chlorinated secondary metabolites derived from a mixed PKS-NRPS biogenetic route, such as the smenamides. Here we report the presence of a biogenetically different compound, smenopyrone (1), a polypropionate containing two -pyrone rings. The structure of smenopyrone, including its relative and absolute stereochemistry, was determined by spectroscopic analysis (NMR, MS, ECD) supported by comparison with model compounds from the literature. Pyrone polypropionates are unprecedented in marine sponges, but are commonly found in marine mollusks, where their biosynthesis by symbiotic bacteria has been hypothesized and at least in one case demonstrated. As pyrones have recently been recognized as bacterial signaling molecules, we speculate that smenopyrone could mediate inter-kingdom chemical communication between S. aurea and its symbiotic bacteria.

Potential distribution models are used to predict the presence and geographic limits of a species as a function of bioclimatic variables. The lack of knowledge of the geographic distribution of species endemic to Mexico is a limiting factor in understanding their ecology, conservation, and potential applications. Distribution models were generated with occurrence data of 11 species of the genus Zephyranthes, 19 bioclimatic and three topographic variables with the Maximum Entropy (MaxEnt) method. The dimensionality reduction analysis (PCA) allowed determining that, of the 19 variables, four contributed the highest percentage to the classification of the models, explaining more than 80% of the accumulated variance. The resulting models were evaluated according to the value of the area under the curve (AUC) and potential distribution models with AUC values &gt;0.89 were obtained. The results suggest that most species are distributed in the biogeographic province of the Transmexican Volcanic Belt. Zephyranthes concolor was the species with the largest potential distribution area. The species with the most restricted potential distribution was Zephyranthes sessilis.

Investments in public transit infrastructure in Latin America and the Caribbean often aim to reduce spatial and social inequalities by improving accessibility to jobs and other opportunities for vulnerable populations. The Metropolitano, Lima’s Bus Rapid Transit (BRT) project had as one of its central goals to connect low-income populations living in the peripheries to jobs in the city center. We examine the contribution of Lima’s BRT system to accessibility to employment in the city, particularly for low-income public transit users. Building on secondary datasets of employment, household socio-demographics and Origin-Destination surveys before and after the BRT began operations, we assess its effects on potential accessibility to employment, comparing impacts amongst lower versus higher income populations. Findings suggest that the BRT line reduced travel times to reach jobs, in comparison with traditional public transport in the city, amongst populations living within walking distance of the system. However, we also find that the coverage of the BRT declines in areas with high concentrations of poor and extreme poor populations, limiting the equitability of the accessibility improvements. We analyze the distributional effects of BRT infrastructure and services, discussing policy avenues that can improve the prospects for BRT system investments to include the poor in their mobility benefits.

Lake ice thickness (LIT) is a sensitive indicator of climate change identified as a thematic variable of Lakes as an Essential Climate Variable (ECV) by the Global Climate Observing System (GCOS). Here, we present a novel and efficient analytically based retracking approach for estimating LIT from high-resolution Ku-band (13.6 GHz) synthetic aperture radar (SAR) altimetry data. The retracker method is based on the analytical modeling of the SAR radar echoes over ice-covered lakes that show a characteristic double-peak feature attributed to the reflection of the Ku-band radar waves at the snow-ice and ice-water interfaces. The method is applied to Sentinel-6 Unfocused SAR (UFSAR) and Fully Focused SAR (FFSAR) data, with their corresponding tailored waveform model, referred to as the SAR_LITand FFSAR_LITretracker, respectively. LIT retrievals from Sentinel-6 SAR data at different posting rates are evaluated against those obtained from thermodynamic lake ice model simulations and Low Resolution Mode (LRM) Sentinel-6 and Jason-3 data over two ice seasons during the tandem phase of the two satellites, allowing precise assessment of the continuity between LRM and SAR LIT retrievals. Consistency checks of the Sentinel-6 SAR LIT estimates are also performed using optical/radar images that provide information on the snow/ice conditions on the same dates. The analysis is performed on Great Slave Lake and Baker Lake (Canada) that differ in terms of lake size, bathymetry, snow/ice properties, and seasonal evolution of LIT. The accuracy of the LIT estimates with the SAR LIT retrackers is on the order of 5 cm once the ice is well established on the lakes, meeting the GCOS requirements of LIT measurement uncertainty, which is a factor of 2 to 3 times better than that of LIT obtained with LRM data, bringing a further improvement compared to previous analyses and methods. The SAR LIT retrackers presented are promising tools for monitoring the inter-annual variability and trends in LIT from current and future SAR altimetry missions.

Predicting trip purpose from comprehensive and continuous smart card data is beneficial for transport and city planners in investigating travel behaviours and urban mobility. Here we propose a framework, ActivityNET, using machine learning (ML) algorithms to predict passengers’ trip purpose from smart card data and Points-of-Interest (POIs) data. The feasibility of the framework is demonstrated in two phases. Phase I focuses on extracting activities from individuals’ daily travel patterns from smart card data and combining them with POIs using the proposed ‘activity-POIs consolidation algorithm’. Phase II feeds the extracted features into an artificial neural network (ANN) with multiple scenarios and predicts trip purpose under primary activities (home and work) and secondary activities (entertainment, eating, shopping, child drop-offs/pick-ups and part-time work) with high accuracy. As a case study, the proposed ActivityNET framework is applied in Greater London and illustrates a robust competence to predict trip purpose. The promising outcomes demonstrate that the cost-effective framework offers high predictive accuracy and valuable insights into transport planning.

Polyamide 11 (PA11) is a plant-based nylon made from castor beans. Powder bed fusion laser sintering (PBF-LS) is an additive manufacturing process used for PA11 which allows the reuse of the unsintered powder. The unsintered powder is mixed with virgin powders at different refresh rates which has been studied extensively for most semi-crystalline polyamides. However, there is lack of information on the effect of using 100% reused PA11 powder and the number of times it is reused on its own during powder bed fusion laser sintering. This paper investigates the effect of reusing PA11 powder in PBF-LS and number of times it is reused on the dimensional accuracy, density, thermal and tensile properties. From 100% virgin powder to 3rd use of the powder, there is a decrease in powder wastage, decrease in crystallinity and tensile strength. These was associated with the polymerisation and cross-linking process of polymer chains, upon exposure to high temperature. This results in a higher molecular weight and hence density. From the 4th use to 10th reuse, the opposite was observed which was associated to an increase in high-viscosity and un-molten particles which resulted in defects in the PBF-LS parts.

Humeral resurfacing arthroplasty (HRA) entails the substitution of the articular surface alone with a prosthetic cap without stem. It is a more conservative procedure which can be easily converted in a total arthroplasty if necessary. The present study aimed to evaluate the clinical and radiographical outcomes in a series of patients treated with HRA. 33 patients with a mean fol-low-up of 11 years were clinically (Constant score; Disability of the Arm, Shoulder and Hand score, DASH) and radiographically assessed before and after surgery. Constant and DASH score improved significantly after surgery, and only 2 cases needed revision surgery. HRA represents a valid therapeutic option in selected cases to improve the quality of life and delaying the need for more invasive procedures.

Participatory landscape conservation is an innovative approach that weaves theory and practice to bridge the gap between theoretical models and practical applications. Intertropical regions as the case of Mexico face challenges to conciliate regional governability, social justice, and nature conservation. The State of Michoacan is one of these regions where the challenges exacerbate since nature conservation is last due to its ongoing territorial disputes. We implemented the participatory landscape conservation approach by creating a complementary form of protected areas with ongoing conflicts, drought conditions, and extreme poverty. We conducted participatory mapping and land cover/use analyses as main methodological tools to reach consensus among stakeholders. We integrated, macro, micro and social scales to provide sound arguments to integrate local, scholar and policy makers perceptions. The outcomes of the participatory mapping analyses were assessed. The present papers provide evidence of the positive outcome of using a Participatory Landscape Conservation to establish a Biosphere Reserve, safeguarding one of the most biologically diverse and delicate ecosystems consisting of seasonally dry tropical forests within a rather disputed region. We discussed the relevance of our findings and compared them to ongoing regional and global trends in the light of other forms of establishing protected areas.

This study re-introduces a protein-free rapid test method for nucleic acids on paper based lateral flow assays utilizing special multichannel nitrocellulose membranes and DNA-Gold conjugates, achieving significantly enhanced sensitivity, easier protocols, reduced time of detection, reduced costs of pro-duction and advanced multiplexing possibilities. It is shown for the first time a protein-free nucleic acid based lateral flow assay (NALFA) with a limit of detection of 1 pmol of DNA. The total production duration of such an assay was successfully reduced from the currently known several days to just a few hours. The simplification and acceleration of the protocol make the method more accessible and practical for various applications. The developed method supports multiplexing, enabling the sim-ultaneous detection of up to six DNA targets. This multiplexing capability is a significant improve-ment over traditional line tests and offers more comprehensive diagnostic potential in a single assay. The approach significantly reduces the run time compared to traditional line tests, which enhances the efficiency of diagnostic procedures. The protein-free aspect of this assay minimizes the prevalent complications of cross-reactivity in immunoassays especially in cases of multiplexing. It is also demonstrated that the NALFA developed in this study is amplification-free and hence does not rely on specialized technicians, nor does it involve labour-intensive steps like DNA extraction and PCR processes. Overall, this study presents a robust, efficient, and highly sensitive platform for DNA or RNA detection, addressing several limitations of current methods documented in the literature. The advancements in sensitivity, cost reduction, production time, and multiplexing capabilities mark a substantial improvement, holding great potential for various applications in diagnostics, forensics, and molecular biology.

The exploitation of the metallacarboranes’ potential in various fields of research and practical ap-plications requires the availability of convenient and versatile methods for their functionalization with various functional moieties and/or linkers of different types and lengths. Herein we report a study on cobalt bis(1,2-dicarbollide) functionalization at 8,8’-boron atoms with different het-ero-bifunctional moieties containing protected hydroxyl function allowing further modification after deprotection. Moreover, an approach to the synthesis of three and four functionalized metallacarboranes, at boron and carbon atoms simultaneously, via additional functionalization at carbon to obtain derivatives carrying three or four rationally oriented and distinct reactive surfaces, is described

Convolutional neural networks (CNNs), inspired by biological visual cortex systems, are a powerful category of artificial neural networks that can extract the hierarchical features of raw data to greatly reduce the network parametric complexity and enhance the predicting accuracy. They are of significant interest for machine learning tasks such as computer vision, speech recognition, playing board games and medical diagnosis [1-7]. Optical neural networks offer the promise of dramatically accelerating computing speed to overcome the inherent bandwidth bottleneck of electronics. Here, we demonstrate a universal optical vector convolutional accelerator operating beyond 10 Tera-FLOPS (floating point operations per second), generating convolutions of images of 250,000 pixels with 8-bit resolution for 10 kernels simultaneously — enough for facial image recognition. We then use the same hardware to sequentially form a deep optical CNN with ten output neurons, achieving successful recognition of full 10 digits with 900 pixel handwritten digit images with 88% accuracy. Our results are based on simultaneously interleaving temporal, wavelength and spatial dimensions enabled by an integrated microcomb source. This approach is scalable and trainable to much more complex networks for demanding applications such as unmanned vehicle and real-time video recognition.

The article describes the use of microwave irradiation in the synthesis of bis(cyclo carbonate) compounds (BCC) in bulk (without solvent) from carbon dioxide capture using an epoxidized compound - a commercial epoxy resin, and compares this process to the conventional method. CO2 cycloaddition to epoxides is an ecological and efficient method for the formation of bis(cyclic carbonates). Moreover, the introduction of gas into the reaction mixture was carried out at atmospheric pressure with a controlled flow rate, which is advantageous from an economic point of view. Progressive structural changes and the presence of characteristic chemical groups were monitored using attenuated total reflectance infrared spectroscopy with Fourier transform. The obtained crude products were purified to obtain three fractions, which were subjected to detailed structural analysis using FT-IR and 13CNMR. The formation of the main product with two cyclic carbonates was confirmed. The presence of monomers, dimers and trimers in individual fractions as well as their thermal stability were determined, and the molecular masses in individual fractions were determined using gel permeation chromatography (GPC).

A Pt(II) complex featuring chelating tridentate bis-aryloxide tetrahydropyrimidinium based N-heterocyclic carbene (NHC) was synthesized and characterized by using different techniques. The electrochemical properties of the complex were investigated by cyclic voltammetry as well as differential pulse voltammetry, which revealed two reversible one-electron oxidation processes. The chemical generation and isolation of one-electron-oxidized species were performed oxidizing the initial complex by means of AgBF4. The combined UV-Vis/NIR- and EPR-spectroscopy studies supported by density functional theory (DFT) calculations suggest the formation of Pt(II)-phenoxyl radical complex. The latter open-shell derivative was structurally characterized by means of X-ray diffraction analysis. Finally, the neutral platinum complex was tested as a mediator in the process of electrocatalytic oxidation of 2-(methylamino)ethanol (MEA).

We investigated the response of leaf photosynthetic capacity to climate warming and its variation among provenances of Larix gmelinii (Dahurian larch). Seedlings of 11 L. gmelinii provenances were transplanted into two common gardens with different climate conditions (control and warming climate). We measured the leaf photosynthetic capacity and explored its influencing factors. The warming treatment significantly increased the maximum net photosynthetic rate (Pmax-a), photosynthetic nitrogen use efficiency (PNUE), maximum carboxylation rate (Vcmax), maximum electron transport rate (Jmax), triose phosphate utilization rate (TPU), mesophyll conductance (gm), leaf nitrogen content (Narea), and chlorophyll content (Chlm). The Pmax-a was significantly positively associated with Vcmax, Jmax, TPU, gm, and Narea, and the slope of the correlations between Pmax-a and Vcmax, Jmax, and TPU was steeper in the warming treatment. The responses of Pmax-a, PNUE, Vcmax, Jmax, TPU, Narea, and Chlm to warming differed among provenances. The effects of warming on Pmax-a, Vcmax, Jmax, and TPU increased and then decreased as the aridity index of the original site increased. Overall, the warming treatment improved the photosynthetic capacity of L. gmelinii, but the extent of the improvement varied among provenances. These findings provide insights into the mechanisms underlying the responses of L. gmelinii to climate warming.

With the inclusion of Internet Gaming Disorder (IGD) in both the DSM-5 and ICD-11, understanding the prevalence and diagnostic discrepancies is crucial for developing appropriate interventions. This study presents a meta-analysis of the prevalence of IGD based on two diagnostic criteria. We systematically searched PubMed, Web of Science databases. 17 studies were included in the final analysis, The analysis incorporated studies employing the DSM-5 and ICD-11 criteria and focused on the impact of various factors, including study location, sample size, and quality score, on the reported prevalence rates using a random-effects model. Heterogeneity and publication bias were analyzed using an I2 test and Galbraith plots , The prevalence of IGD varied among the selected studies, with a general pooled prevalence of 5% (95% CI: 3%–7%). Subgroup analysis indicated that the prevalence rates of IGD (DSM-5 criteria) and GD (ICD-11 criteria) do not show significant differences. DSM-5-based scales yielded varied results, while heterogeneity among the studies was high (I2 = 98.50). In contrast, ICD-11-based scales produced more consistent and less variable findings. Our findings highlight that assessment scales, not diagnostic criteria, impact IGD prevalence. This underscores the importance of adopting standardized methodologies to guide public health interventions. However, given the limited research based on ICD-11 diagnostic criteria, further investigation is necessary to determine the variations in prevalence rates of IGD under different diagnostic standards.

Children’s motor competence (MC) has declined in the past decades, while sedentary behavior (SB) has increased. This study examined the association between MC and physical activity (PA) levels among primary schoolchildren. Demographics, body height and weight, MC (Athletic Skills Track) and PA levels (ActiGraph, GT3X+) were assessed among 595 children (291 boys, mean age = 9.2 years, SD = 1.1). MC was standardized into five categories: from very low to very high. PA levels were classified into sedentary behavior (SB), light physical activity (LPA), and moderate-to-vigorous physical activity (MVPA). Mixed model analyses were conducted with PA levels as dependent variables and MC as the independent variable, while adjusting for age, gender, and BMI z-score on the individual level. Additional moderation analyses between covariates and MC and PA levels were also conducted. A negative association between MC and SB (β = -3.17) and a positive association between MC and MVPA (β =1.41) were found. The strength of both associations increased as children expressed lower or higher levels of MC. Increased age and being a girl were significant predictors of higher levels of SB and lower levels of MVPA. Non-overweight children spent significantly more minutes in MVPA compared with overweight children. No moderating effects of BMI, gender, and age were found on the association between MC and PA levels. MC is an important correlate of both SB and MVPA, particularly for children with very high or low MC. Developing and improving children’s MC may contribute to spending less time in SB and more time in MVPA, particularly for high-risk groups, i.e. children with low MC. Moreover, addressing MC development and PA promotion simultaneously might create positive feedback loops for both children’s MC and PA levels.

Given the financial demands of attending college, the transition to new living situations, abrupt changes in social support, and overall lifestyle adjustments, college students are at an increased risk of food insecurity (FI) compared to the general population. Collegiate athletes experience an even greater risk of FI as a result of greater time commitments and energy demands associated with their sports. This heightened vulnerability poses a tremendous threat to student-athletes’ academic and athletic achievements. This study aims to address the prevalence and primary determinants of FI among collegiate athletes while providing potential solutions to navigate and alleviate the effects of diminished food security among this demographic. To address these aims, a total of 18 articles were selected from both peer-reviewed and gray literature. The U.S. Household Food Security Survey Module (US-HFSSM) survey tools were predominantly utilized across universities throughout the United States to gather data on FI. Student-athletes reported experiencing FI across various regions of the United States, including universities in northeastern states (n=5), the southwest region (n=3), the southeast region (n=3), the northwest (n=1), and the Midwest (n=1). Overall, FI prevalence rates ranged from 9.9% to 65% and the most significant contributors included limited financial resources, time management, meal plans, and housing location/amenities. These findings highlight a need for screening, education, and intervention to address FI among collegiate athletes.

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

This paper proposes an innovative mechatronic piezo-actuated module to control vibrations in modern machine tools. Vibrations represent one of the main issues that compromise seriously the quality of the workpiece. The active vibration control (AVC) device is composed by a host part integrated with sensors and actuators synchronized by a regulator, able to make a self-assessment and adjust to the environmental alteration. This study presents the mechatronic model based on the kinematic and dynamic analysis of the AVC device. To ensure a real time performance, a H2-LQG controller has been developed and validated by simulations involving machine tool, PZT actuator and controller models. The Hardware-in-the-loop (HIL) architecture is adopted to control and attenuate the vibrations. A set of experimental tests has been performed to validate the AVC module on a commercial machine tool. The feasibility of the real time vibration damping is demonstrated and the simulation accuracy is evaluated.

The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows to form constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is endorsed by pi-staking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)‐silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6–, BF4–, SbF6–, ClO4–, NTf2–, OTf2–. These compounds were characterized in the solid-state by single crystal XRD and reflectance spectra, and in solution by 1H NMR, mass spectrometry, electroanalysis and UV-visible absorption spectroscopy. The X-ray diffraction (XRD) structure of complexes {[Ag(3)][PF6]}∞ (4) and {[Ag(3)][SbF6]∞ (6), where 3 is 3,3'-[(1,1'-biphenyl)-2,2'-diyl]-6,6'-bis[phenyl]-1,2,4,5-tetrazine, revealed the formation of 1D polymeric chains, characterized by an evolution to a large opening of the original tweezer and a coordination of silver(I) via two chelating nitrogen atom and some C=C pi-interactions. Electrochemical and UV spectroscopic properties of the original tweezer and of the corresponding silver complex are reported and compared. 1H NMR titrations with AgNTf2 allowed to determine the stoichiometry, and apparent stability of two solution species, namely [Ag(3)]+ and [Ag(3)2]2+, that formed in CDCl3/CD3OD 2:1 v/v mixtures.

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

We investigated the micro-threaded stem taper surface and the impact on premature failures, aseptic loosening, and infection. We have focused on the fretting, and crevice corrosion of micro-threaded tapers, as well as the characterization of microstructure and surface properties of two new and three retrieved Zweymüller stem tapers of cementless hip endoprostheses selected from a set of 45 stems. The retrievals examined were those in which the sole source of modularity with a metallic component was the head-stem taper interface between the Ti alloy taper stem and the ceramic head. To determine the surface chemistry and microstructures of both new and retrieved hip endoprostheses stem taper titanium alloy, scanning electron microscopy (SEM) was employed for morphological and microstructural analyses. At the same time, energy dispersive spectroscopy (EDS) was utilized for characterizing chemical element distribution, and electron backscattered diffraction (EBSD) was used for phase analysis. The micro-threated stem taper’s roughness for different manufacturers was investigated using an optical profilometer. Standard roughness pa-rameters Ra (average surface roughness) and Rz (mean peak to valley height of the roughness pro-file) were used in this investigation.Additionally, profile depth and peak spacing for different samples were investigated. The surface roughness results indicate no significant difference in roughness associated with varying survivorship times, ranging from 3 to 239 months, and across different manufacturers. Electrochemical studies revealed no fretting corrosion in retrieved stem tapers (ceramic head) that prematurely failed due to aseptic loosening after 239 months, infection after 3 months, and low-grade infection after a 32-month lifetime. Therefore, three retrieved ta-pers and two new ones for comparison underwent potentiodynamic measurements in Hank’s so-lution to ascertain the corrosion rate of new and retrieved stem taper surfaces. The results show a low corrosion rate for both new and retrieved samples that failed prematurely due to aseptic loosening. However, the corrosion rate of infected and low-grade infected tapers was higher. In conclusion, our study aligns with existing literature, suggesting that the use of ceramic heads de-creases the problem of taper corrosion and subsequently reduces premature failures in total hip arthroplasty.

Various attempts to amplify an AQP11 cDNA from tissues of the spiny dogfish (Squalus acanthias) were made. Two pairs of deoxy-inosine-containing degenerate primers were designed based on conserved amino acid sequences from an AQP11 alignment. These primers yielded some faint bands from gill cDNA that were sequenced. Blast searches with the sequences showed they were not AQP11. An elasmobranch AQP11 nucleotide sequence alignment was produced to identify conserved regions to make further degenerate primers. One primer pair produced a short 148bp fragment showing particularly strong expression in gill and intestine. It was sequenced and represented a piece of the AQP11 gene. However, as the fragment may have resulted from contaminating genomic DNA (in total RNA used to make cDNA), 5’ and 3’ RACE was performed to amplify the two ends of the putative cDNA. 5’ and 3’ RACE amplifications depend on the presence of a 5’ cap nucleotide and a poly A tail respectively on the putative AQP11 mRNA. Hence successful amplification was only possible from cDNA and not genomic DNA. Nested RACE amplifications were performed using gill and intestinal RACE cDNA but none of the DNA fragments were AQP11. Consequently, the spiny dogfish AQP11 gene may represent a pseudogene.

The hydrothermal synthesis of aluminophosphate molecular sieve type AlPO4-11 was processed from chemicals containing psueudobohemite, 85% phosphoric acid, water, and di-isopropylamine as templating agent. The crystallization of the samples was studied by taking samples in times from 2 to 74 hours. The obtained white powder products have been characterized by XRD patterns, FT-IR spectra, thermogravimetric data, scanning electron microscopy and pH measurement of the mother liquor. The pore volume, as determined from TG and DTG curves, was ca. 0.17 cm3g-1. The crystallization process of the aluminophosphate exhibited in its initial phase a behavior of first order reaction with a specific velocity constant of ca. 0.25 h-1, as determined from XRD and FT-IR data.

There is much discussion regarding the Sustainable Development Goals’ (SDGs) capacity to promote inclusive development. While some argue that they represent an opportunity for collaborative goal-led and evidence-based governance, other voices express concerns as they perceive them as techno-managerial framework, that measures development according to quantitatively defined parameters and does not allow for local variation. We argue that the extent to which the positive or negative aspects of the SDGs prevail depends on the monitoring system’s ability to account for multiple and intersecting inequalities. Attention to the role of inequalities for SDG monitoring is of particular importance for SDG 11 due to the additional methodological challenge posed by the need for sub-nationally (urban) representative indicators – especially in cities with intra-urban inequalities related to socio-spatial variations among neighbourhoods. Investigating the extent to which its representativeness is vulnerable to inequalities we systematically analyse the current methodological proposals for the SDG 11 indicator framework. The outcome is a call for 1) a more explicit attention to intra-urban inequalities, 2) the development of a methodological approach to “recalibrate” the city-level indicators to account for the degree of intra-urban inequalities, and 3) an alignment between methodologies and data practices applied for monitoring SDG 11 and the extent of the underlying inequalities within the city that is being assessed. This would enable an informed decision regarding the trade-off in indicator representativeness between conventional data sources, such as censuses and household surveys, and emerging methods, such as participatory geospatial methods and citizen-generated data practices.

Epoxy matrix composites reinforced with high-performance fibers such as carbon, Kevlar, and glass, exhibit excellent specific stiffness and strength in many mechanical applications. However, these composites are disappointingly non-recyclable and are usually disposed of in landfill sites, with no realistic prospect for biodegradation in reasonable time. In contrast, moldable composites with carbonized elastomeric matrices developed in the last decades possess attractive mechanical properties in final net-shape products and can also be incinerated or recycled. Many carbon and inorganic fillers have recently been evaluated to adjust the properties of carbonized elastomeric composites. Renewable organic fillers such as human or animal hair offer an attractive fibrous material with substantial potential for reinforcing composites with elastomeric matrices. Samples of unidirectional fiber composites (with hair volume fraction up to 7 %) and quasi-isotropic short fiber composites (with hair volume fraction up to 20 %) of human hair-reinforced nitrile butadiene rubbers (HH-NBR) were produced in the peroxide-cured and carbonized states. The samples were characterized using SEM, Raman spectroscopy and photoacoustic microscopy. Mechanical tests were performed in tension using a miniature universal testing machine. The expected effect of fiber reinforcement on the overall mechanical performance has been demonstrated for both cured and carbonized composites. Considerable enhancement of the elastic modulus (up to 10 times), ultimate tensile strength (up to 3 times) and damage tolerance was achieved. The evidence of satisfactory interfacial bonding between hair and rubber was confirmed by SEM imaging of fracture surfaces. The suitability of photoacoustic microscopy was assessed for 3D reconstruction of the fiber sub-system spatial distribution and non-destructive testing.