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Time-averaged restraints from nuclear magnetic resonance (NMR) measurements have been implemented in the UNRES coarse-grained model of polypeptide chains in order to develop a tool for data-assisted modeling of the conformational ensembles of multistate proteins, intrinsically disordered proteins (IDPs) and proteins with intrinsically disordered regions (IDRs), many of which are essential in cell biology. A numerically stable variant of molecular dynamics with time-averaged restraints has been introduced, in which the total energy is conserved in sections of a trajectory in microcanonical runs, the bath temperature is maintained in canonical runs, and the time-average-restraint-force components are scaled up with the length of the memory window so that the restraints affect the simulated structures. The new approach restores the conformational ensembles used to generate ensemble-averaged distances, as demonstrated with synthetic restraints. The approach results in a better fitting of the ensemble-averaged interproton distances to those determined experimentally for multistate proteins and proteins with intrinsically disordered regions, which puts it at an advantage over all-atom approaches with regard to the determination of the conformational ensembles of proteins with diffuse structures, owing to a faster and more robust conformational search.

A robust analytical method was developed for the determination of per- and polyfluoroalkyl substances (PFAS) in e-cigarette refill liquids using solid-phase extraction (SPE) with weak anion-exchange sorbent, followed by detection with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The design of experiment approach was employed to optimize sample preparation, leading to the validation of the method with limits of detection for PFAS ranging from 0.24 to 1.1 pg/mL. The method demonstrated inter-day repeatability of <17 % and relative recovery values between 89 % and 123 %. Additionally, the study explored the composition of e-cigarette refill liquids, focusing on the concentrations of primary constituents, such as vegetable glycerine and propylene glycol. Direct PFAS exposure through e-cigarette use might be of significant health concern due to vaping. Additionally, such products may serve as new source of PFAS release raising emerging issues about environment. Potential PFAS contamination in e-cigarette refill liquids may include manufacturing processes, packaging materials, or components of the e-cigarette devices, in result, leading to exposure during inhalation. A total of 31 e-cigarette refill liquid samples from various brands were analysed, revealing that PFAS were present mainly at trace levels. However, elevated concentrations exceeding 25 pg in 1 mL of commercial e-cigarette refill liquids were determined for PFNA, PFHxA, PFBS, HFPO-DA (GenX), and N-EtFOSAA. Among these, PFBS exhibited the highest detection frequency, occurring in 39 % of the samples. Notably, at least one of PFAS compounds was detected in 84 % of the samples analysed. Moreover, the higher PFAS content was determined in e-cigarette refill liquids with a nicotine content of 20 mg/mL than those with 6 mg/mL., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The procedure for determining the maximum power of a single-junction photovoltaic cell operating in various types of lighting is presented. This is a key issue for photovoltaics powering the mobile Internet-of-Things (IoT). The simulations performed are based on the detailed balance principle, without any of the simplifying assumptions included in the Shockley-Queisser model. Optimal energy bandgap for diffuse solar light was found to be 1.64 eV with a cutoff generated power of 37.3 W/m 2 . For the LED lighting considered in this work, the optimal energy bandgap and maximum power limit are 1.86 eV, 1.63 W/m 2 , and 1.79 eV, 1.51 W/m 2 for cool and warm lighting, respectively, at 900 lux. Considering that the maximum power limit of diffuse solar radiation is much higher than the limit for LED lighting, we concluded that 1.64 eV is the optimal bandgap for most mobile IoT devices operating outdoors all or almost all the time., Competing Interests: The authors declare no competing financial interests., (© 2024 The Author(s).)

The oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) are critical processes in water splitting, yet achieving efficient performance with minimal overpotential remains a significant challenge. Although NiFe-based catalysts are widely studied, their performance can be further enhanced by optimizing the interaction between the catalyst and the substrate. Here, we present a detailed investigation of NiFe-modified graphite electrodes, comparing the effects of compressed and expanded graphite substrates on catalytic performance. Our study reveals that substrate geometry plays a pivotal role in catalyst distribution and activity, with expanded graphite facilitating more effective electron transfer and active site utilization. Additionally, we observe that increasing the NiFe loading leads to only modest gains in performance, due to catalyst agglomeration at higher loadings. The optimized NiFe-graphite composites exhibit superior stability and catalytic activity, achieving lower overpotentials and higher current densities, making them promising candidates for sustainable hydrogen production via alkaline electrolysis.

The interactions of electrons with molecular systems under various conditions are essential to interdisciplinary research fields extending over the fundamental and applied sciences. In particular, investigating electron-induced ionization and dissociation of molecules may shed light on the radiation damage to living cells, the physicochemical processes in interstellar environments, and reaction mechanisms occurring in combustion or plasma. We have, therefore, studied electron-induced ionization and dissociation of the gas phase 3,4-dihydro-2H-pyran (DHP), a cyclic ether appearing to be a viable moiety for developing efficient clinical pharmacokinetics and revealing the mechanisms of biofuel combustion. The mass spectra in the m/z = 10-90 mass range were measured at several different energies of the ionizing electron beam using mass spectrometry. The mass spectra of DHP at the same energies were simulated using on-the-fly semi-classical molecular dynamics (MD) within the framework of the QCxMS formalism. The MD settings were suitably adjusted until a good agreement with the experimental mass spectra intensities was achieved, thus enabling a reliable assignment of cations and unraveling the plausible fragmentation channels. Based on the measurement of the absolute total ionization cross section of DHP (18.1 ± 0.9) × 10-16 cm2 at 100 eV energy, the absolute total and partial ionization cross sections of DHP were determined in the 5-140 eV electron energy. Moreover, a machine learning algorithm that was trained with measured cross sections from 25 different molecules was used to predict the total ionization cross section for DHP. Comparison of the machine learning simulation with the measured data showed acceptable agreement, similar to that achieved in past predictions of the algorithm., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Molecular imprinting technology is well established in areas where a high selectivity is required, such as catalysis, sensing, and separations/sample preparation. However, according to the Principles of Green Chemistry, it is evident that the various steps required to obtain molecularly imprinted polymers (MIPs) are far from ideal. In this regard, greener alternatives to the synthesis of MIPs have been proposed in recent years. However, although it is intuitively possible to design new green MIPs, it would be desirable to have a quantitative measure of the environmental impact of the changes introduced for their synthesis. In this regard, this work proposes, for the first time, a metric tool and software (termed AGREEMIP) to assess and compare the greenness of MIP synthesis procedures. AGREEMIP is based on 12 assessment criteria that correspond to the greenness of different reaction mixture constituents, energy requirements, and the details of MIP synthesis procedures. The input data of the 12 criteria are transformed into individual scores on a 0-1 scale that in turn produce an overall score through the calculation of the weighted average. The assessment can be performed using user-friendly open-source software, freely downloadable from mostwiedzy.pl/agreemip. The assessment result is an easily interpretable pictogram and visually appealing, showing the performance in each of the criteria, the criteria weights, and overall performance in terms of greenness. The application of AGREEMIP is presented with selected case studies that show good discrimination power in the greenness assessment of MIP synthesis pathways., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A simple smartphone-based digital image colorimetry was proposed for the determination of total capsaicinoid content and the assessment of chili pepper pungency. The biobased solvent D-limonene was used for the first time to isolate analytes. Capsaicinoids were efficiently separated from chili pepper by solid-liquid extraction with D-limonene followed by partitioning of the analytes into the ammonium hydroxide solution to eliminate the matrix interference effect. For colorimetric detection of total capsaicinoid content, a selective chromogenic reaction was performed using Gibbs reagent (2,6-dichloroquinone-4-chloroimide). Measurements were performed using a smartphone-based setup and included image analysis with the program ImageJ. The limit of detection of the proposed procedure was 0.15 mg g -1 . The intra-day repeatability did not exceed 10.0 %. The inter-day repeatability was less than 16.5 %. The comparison of the smartphone-based procedure with high-performance liquid chromatography showed satisfactory results., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Propolis extracts have been used in traditional medicines since ages due to its advantageous complex chemical composition. However, the antibacterial and antifungal activity of poplar propolis extracts prepared in Natural Deep Eutectic Solvent (NADES) are seldom studied. This study investigates suitable alternate for ethanol as a solvent for extraction for Polish poplar propolis. It also attempts to identify suitable extraction condition for the efficient transfer of compounds from propolis to the solvents. The extraction efficiency of NADES extracts was assessed in terms of total phenolic content, antioxidant activity and antimicrobial activity. The chemical composition of the extracts was analysed using UHPLC-DAD-QqTOF-MS. Four extracts, prepared in Propylene Glycol, Choline Chloride:Propylene Glycol (1:3), Choline Chloride:Propylene Glycol (1:4) and Choline Chloride:Glycerol (1:2), demonstrated activity and properties similar to ethanolic extract and extraction at 50 °C was found the most suitable for propolis. HPLC analysis confirmed that the chemical cocktail extracted by these solvents from propolis were identical with minor variations in their concentration as compared to its ethanolic extract. Thus, extracts of propolis at 50 °C in Propylene Glycol, Choline Chloride:Propylene Glycol (1:3) and Choline Chloride:Propylene Glycol (1:4) can be alternates for ethanolic extracts., (© 2024. The Author(s).)

Compositionally complex oxides (CCOs) or high-entropy oxides (HEOs) are new multielement oxides with unexplored physical and functional properties. In this work, we report fluorite structure-derived compositionally complex zirconia with composition Zr 1- x (Gd 1/5 Pr 1/5 Nd 1/5 Sm 1/5 Y 1/5 ) x O 2-δ ( x = 0.1 and 0.2) synthesized in solid-state reaction route and sintered via hot pressing at 1350 °C. We explore the evolution of these oxides' structural, microstructural, mechanical, electrical, and electromechanical properties regarding phase separation and sintering mechanisms. Highly dense ceramics are achieved by bimodal mass diffusion, composing nanometric tetragonal and micrometric cubic grains microstructure. The material exhibits an anomalously large electrostriction response exceeding the M 33 value of 10 -17 m 2 /V 2 at room temperature and viscoelastic properties of primary creep in nanoindentation measurement under fast loading. These findings are strikingly similar to those reported for doped ceria and bismuth oxide derivates, highlighting the presence of a large concentration of point defects linked to structural distortion and anelastic behavior, which are characteristics of nonclassical ionic electrostrictors.

The baby disposable diapers were investigated as a sampling material for urine collection and validated for the evaluation of the exposure of children to xenobiotics. Phthalate metabolites detected in urine samples were chosen as proof-of-concept analytes. For the determination of phthalate metabolites in children's urine samples, high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) was used. Two sampling approaches were compared, namely sterile containers and baby disposable diapers. Thirty urine samples from infants and toddlers were analyzed by both methods in parallel and the results were compared. It was found that for diaper sampling, lower concentrations of the metabolites were observed, however, the general distribution for particular metabolites remains the same for both methods. For most of the metabolites high determination coefficients were obtained, namely 0.9929 for MEHHP, 0.9836 for MMP, 0.9796 for MECPP, and 0.9784 for 2-cx-MMHP. For MEOHP the determination correlation coefficient was 0.9154, while for MBP was - 0.7771 and MEHP was - 0.5228. In general, for diaper sampling an underestimation for 2-cx-MMHP and MEOHP was observed, while for MMP diaper-based approach provides overestimation. However, the proposed procedure confirms the possibility of using baby disposable diapers as a material for the collection of urine samples for biomonitoring purposes and fast screening of phthalates exposure., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The most effective method for determining the coordinates of the railway track axis is based on using mobile satellite measurements. However, there are situations in which the satellite signal may be disturbed (due to field obstructions) or completely disappear (e.g., in tunnels). In these situations, the ability to measure the value of the directional angle of a moving rail vehicle using an inertial system is useful. The directional angle is determined on a topographic map as the angle between the direction of the vehicle's longitudinal axis (or the direction of a tangent to the track axis) and the reference direction, which is the north. This article presents a method for determining the directional angle of a railway line based on appropriate measurement data. The latter should be Cartesian coordinates of the track axis, allowing for the visualization of a given railway route and permitting a general orientation of its course to be obtained. The presented proposal for solving the problem refers to the assumptions made in the method for determining the curvature of the railway track axis using the moving chord. The assumptions of the proposed method for determining the directional angle of the railway route are discussed, along with the appropriate computational algorithms. The accuracy of this method is assessed using the adopted model geometric layout. Reference is also made to the appropriate method for determining the curvature of the railway track axis. In conclusion, we provide an example of determining the directional angle based on measurement data.

MnCo 1.5 Fe 0.5 O 4 spinel oxide was synthesized using the sol-gel technique, followed by heat treatment at various temperatures (400, 600, 800, and 1000 °C). The prepared materials were examined as anode electrocatalysts for water-splitting systems in alkaline environments. Solid-state characterization methods, such as powder X-ray diffraction and X-ray absorption spectroscopy (XAS), were used to analyze the materials' crystallographic structure and surface characteristics. The intrinsic activity of the MnCo 1.5 Fe 0.5 O 4 was fine-tuned by altering the electronic structure by controlling the calcination temperature, and the highest activity was observed for the sample treated at 800 °C. A shift in the valence state of surface cations under oxidative conditions in an alkaline solution during the oxygen evolution reaction was detected through ex situ XAS measurements. Moreover, the influence of the experimental conditions on the electrocatalytic performance of the material, including the pH of the electrolyte and the temperature, was demonstrated., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Bacillus species isolated from Polish bee pollen (BP) and bee bread (BB) were characterized for in silico probiotic and safety attributes. A probiogenomics approach was used, and in-depth genomic analysis was performed using a wide array of bioinformatics tools to investigate the presence of virulence and antibiotic resistance properties, mobile genetic elements, and secondary metabolites. Functional annotation and Carbohydrate-Active enZYmes (CAZYme) profiling revealed the presence of genes and a repertoire of probiotics properties promoting enzymes. The isolates BB10.1, BP20.15 (isolated from bee bread), and PY2.3 (isolated from bee pollen) genome mining revealed the presence of several genes encoding acid, heat, cold, and other stress tolerance mechanisms, adhesion proteins required to survive and colonize harsh gastrointestinal environments, enzymes involved in the metabolism of dietary molecules, antioxidant activity, and genes associated with the synthesis of vitamins. In addition, genes responsible for the production of biogenic amines (BAs) and D-/L-lactate, hemolytic activity, and other toxic compounds were also analyzed. Pan-genome analyses were performed with 180 Bacillus subtilis and 204 Bacillus velezensis genomes to mine for any novel genes present in the genomes of our isolates. Moreover, all three isolates also consisted of gene clusters encoding secondary metabolites.

(1) Background: In this study, we evaluated the modulation of urine glycosaminoglycans (GAGs), which resulted from etanercept (ETA) therapy in patients with juvenile idiopathic arthritis (JIA) in whom methotrexate therapy failed to improve their clinical condition. (2) Methods: The sulfated GAGs (sGAGs, by complexation with blue 1,9-dimethylmethylene), including chondroitin-dermatan sulfate (CS/DS) and heparan sulfate (HS), as well as non-sulfated hyaluronic acid (HA, using the immunoenzymatic method), were determined in the blood of 89 children, i.e., 30 healthy children and 59 patients with JIA both before and during two years of ETA treatment. (3) Results: We confirmed the remodeling of the urinary glycan profile of JIA patients. The decrease in the excretion of sGAGs ( p < 0.05), resulting from a decrease in the concentration of the dominant fraction in the urine, i.e., CS/DS ( p < 0.05), not compensated by an increase in the concentration of HS ( p < 0.000005) and HA ( p < 0.0005) in the urine of patients with the active disease, was found. The applied biological therapy, leading to clinical improvement in patients, at the same time, did not contribute to normalization of the concentration of sGAGs ( p < 0.01) in the urine of patients, as well as CS/DS ( p < 0.05) in the urine of sick girls, while it promoted equalization of HS and HA concentrations. These results indicate an inhibition of the destruction of connective tissue structures but do not indicate their complete regeneration. (4) Conclusions: The metabolisms of glycans during JIA, reflected in their urine profile, depend on the patient's sex and the severity of the inflammatory process. The remodeling pattern of urinary glycans observed in patients with JIA indicates the different roles of individual types of GAGs in the pathogenesis of osteoarticular disorders in sick children. Furthermore, the lack of normalization of urinary GAG levels in treated patients suggests the need for continued therapy and continuous monitoring of its effectiveness, which will contribute to the complete regeneration of the ECM components of the connective tissue and thus protect the patient against possible disability.

The dissociative double photoionization of isoxazole molecules has been investigated experimentally and theoretically. The experiment has been carried out in the 27.5-36 eV photon energy range using vacuum ultraviolet (VUV) synchrotron radiation excitation combined with ion time-of-flight (TOF) spectrometry and photoelectron-photoion-photoion coincidence (PEPIPICO) technique. Five well-resolved two-body dissociation channels have been identified in the isoxazole's coincidence maps, and their appearance energies have been determined. The coincidence yield curves of these dissociation channels have been obtained in the photon energy ranges from their appearance energies up to 36 eV. The double photoionization of isoxazole produces a C 3 H 3 NO 2+ transient dication, which decomposes into fragments differing from previously reported photofragmentation products of isoxazole. We have found no evidence of pathways leading to the C 3 H 2 NO + , HCN + , C 2 H 2 O + , C 3 HN + , or C 2 H 2 + fragments or their neutral counterparts that have been observed in previous neutral photodissociation and single photoionization studies. Instead, the dissociation of isoxazole after the ejection of two electrons is bond-selective and is governed by two reactions, HCO + + H 2 CCN + and H 2 CO + + HCCN + , whose appearance energies are 28.6 (±0.3) and 29.4 (±0.3) eV, respectively. A third dissociation channel turns out to be a variant of the most intense channel (HCO + + H 2 CCN + ), where one of the fragment ions contains a heavy isotope. Two minor dissociation channels occurring at higher energies, CO + + CH 3 CN + and CN + + H 3 CCO + , are also identified. The density functional and ab initio quantum chemical calculations have been performed to elucidate the dissociative charge-separating mechanisms and determine the energies of the observed photoproducts. The present work unravels hitherto unexplored photodissociation mechanisms of isoxazole and thus provides deeper insight into the photophysics of five-membered heterocyclic molecules containing two heteroatoms.

The sustainable use of baby disposable diapers is one of the issues currently being discussed to reduce the undesirable impact on the environment and improve the public's understanding of the proper use of diapers. This issue is a step toward promoting a cleaner, greener, and waste-less environment. In this article, the authors discuss options for a viable future for both people and the planet. We believe that it inspire others in the field of sustainable use of diapers as well as future education in this area. In addition, we believe that it will be a motivation for a researchers working in industry to be focused on the production of new, biodegradable baby diapers as well as on recycling baby diapers waste (for example as composite material for a structural and architectural component of the building)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

For many organisms, metallophores are essential biogenic ligands that ensure metal scavenging and acquisition from their environment. Their identification is challenging in highly organic matter rich environments like peatlands due to low solubilization and metal scarcity and high matrix complexity. In contrast to common approaches based on sample modification by spiking of metal isotope tags, we have developed a two-dimensional (2D) Solid-phase extraction-Liquid chromatography-mass spectrometry (SPE-LC-MS) approach for the highly sensitive (LOD 40 fmol per g of soil), high-resolution direct detection and identification of metallophores in both their noncomplexed (apo) and metal-complexed forms in native environments. The characterization of peat collected in the Bernadouze (France) peatland resulted in the identification of 53 metallophores by a database mass-based search, 36 among which are bacterial. Furthermore, the detection of the characteristic (natural) metal isotope patterns in MS resulted in the detection of both Fe and Cu potential complexes. A taxonomic-based inference method was implemented based on literature and public database (antiSMASH database version 3.0) searches, enabling to associate over 40% of the identified bacterial metallophores with potential producers. In some cases, low completeness with the MIBiG reference BCG might be indicative of alternative producers in the ecosystem. Thus, coupling of metallophore detection and producers' inference could pave a new way to investigate poorly documented environment searching for new metallophores and their producers yet unknown.

A reliable representation of local interactions is critical for the accuracy of modeling protein structure and dynamics at both the all-atom and coarse-grained levels. The development of local (mainly torsional) potentials was focused on careful parametrization of the predetermined (usually Fourier) formulas rather than on their physics-based derivation. In this Perspective we discuss the state-of-the-art methods for modeling local interactions, including the scale-consistent theory developed in our laboratory, which implies that the coarse-grained torsional potentials inseparably depend on the virtual-bond angles adjacent to a given dihedral and that multitorsional terms should be considered. We extend the treatment to split the residue-based torsional potentials into the site-based regular and improper torsional potentials. These considerations are illustrated with the revised torsional potentials and improper-torsional potentials involving the l-alanine residue and the improper-torsional potential corresponding to serine-residue enantiomerization. Applications of the new approach in coarse-grained modeling and revising all-atom force fields are discussed.

The aim of this study was the whole-genome analysis and assessment of the antimicrobial potential of bacterial isolates from honey harvested in one geographical location-the north of Poland. In total, 132 strains were derived from three honey samples, and the antimicrobial activity of CFAM (cell-free after-culture medium) was used as a criterion for strain selection and detailed genomic investigation. Two of the tested isolates (SZA14 and SZA16) were classified as Bacillus paralicheniformis, and one isolate (SZB3) as Bacillus subtilis based on their ANI and phylogenetic analysis relatedness. The isolates SZA14 and SZA16 were harvested from the same honey sample with a nucleotide identity of 98.96%. All three isolates have been found to be potential producers of different antimicrobial compounds. The secondary metabolite genome mining pipeline (antiSMASH) identified 14 gene cluster coding for non-ribosomal peptide synthetases (NRPs), polyketide synthases (PKSs), and ribosomally synthesized and post-translationally modified peptides (RiPPs) that are potential sources of novel antibacterials. The BAGEL4 analysis revealed the presence of nine putative gene clusters of interest in the isolates SZA14 and SZA16 (including the presence of six similar clusters present in both isolates, coding for the production of enterocin Nkr-5-3B, haloduracin-alpha, sonorensin, bottromycin, comX2, and lasso peptide), and four in B. subtilis isolate SZB3 (competence factor, sporulation-killing factor, subtilosin A, and sactipeptides). The outcomes of this study confirm that honey-derived Bacillus spp. strains can be considered potential producers of a broad spectrum of antimicrobial agents. KEY POINTS: • Bacteria of the genus Bacillus are an important component of honey microbiota. • Honey-derived Bacillus spp. strains are potential producers of new antimicrobials., (© 2023. The Author(s).)

Soil is one of the most important farming resources. Appropriate managing of its quality promotes productive and sustainable agriculture. The valuable farm practice in soil quality managing is based on regular soil analysis with the aim of determining the exact amount of nutrients or other chemical, physical, and biological soil properties. Soil analysis usually requires sample collection at the desired sampling depth followed by sample delivery to chemical laboratories. However, laboratory analyses are resource-intensive and costly, and require a lot of time, effort, and equipment. A low-cost, fast, and effective alternative for soil quality control is the application of smartphones to perform chemical analyses directly in the field or on the farm. In this paper, an overview of recent developments on smartphone-based methodologies for agricultural purposes and portable evaluation of soil quality and its properties is presented. The discussion focuses on recent applications of smartphone-based devices for the determination of basic soil parameters, content of organic matter, mineral fertilizers, and organic or inorganic pollutants. Obvious advantages of using smartphones, such as convenience and simplicity of use, and the main shortcomings, such as relatively poor precision of the results obtained, are also discussed. The general trend shows the huge interest from researchers to move the technology into the field with the aim of providing cost-effective and rapid soil analysis. This paper can broaden the understanding of using smartphones for chemical analysis of soil samples, as it is a relatively new area and is expected to be developed rapidly., (© 2023. The Author(s).)

Formation of plasmonically active silver, copper and composite silver-copper nanostructures were studied in this paper. Metallic nanostructures were fabricated by thermal disintegration, so called dewetting, of the thin films in an argon atmosphere. The formation process of the nanostructures was in-situ observed by a novel method, based on resistance measurements. The influence of the material and thickness of the initial thin film on temperature of their disintegration was investigated. Electrical measurements were validated by scanning electron microscopy observations, while metallic the behavior of nanostructures was studied by XPS method. The formation of silver-copper nanocomposite structures was confirmed by UV-vis spectroscopy. Plasmon resonance with two characteristic peaks for nanocomposite structures was observed., (© 2023. The Author(s).)

The four most popular water models in molecular dynamics were studied in large-scale simulations of Brownian motion of colloidal particles in optical tweezers and then compared with experimental measurements in the same time scale. We present the most direct comparison of colloidal polystyrene particle diffusion in molecular dynamics simulations and experimental data on the same time scales in the ballistic regime. The four most popular water models, all of which take into account electrostatic interactions, are tested and compared based on yielded results and resources required. Three different conditions were simulated: a freely moving particle and one in a potential force field with two different strengths based on 1 pN/nm and 10 pN/nm. In all cases, the diameter of the colloidal particle was 50 nm. The acquired data were compared with experimental measurements performed using optical tweezers with position capture rates as high as 125 MHz. The experiments were performed in pure water on polystyrene particles with a 1 μm diameter in special microchannel cells., Competing Interests: The authors declare no conflict of interest.

We quantified galactosaminoglycans (GAAGs), oligomeric cartilage matrix protein (COMP), and human cartilage glycoprotein 39 (YKL-40) in blood obtained from juvenile idiopathic arthritis (JIA) before and during 2-year treatment with etanercept (ETA), as potential biomarkers of cartilage extracellular matrix (ECM) dysfunction and indicators of efficacy of biologic therapy. We also evaluated the relationship of the mentioned markers with the factors that regulate their metabolism, disintegrin and thrombospondin motif metalloproteinases 4 (ADAMTS4), ADAMTS5, and platelet-derived growth factor BB (PDGF-BB)., Methods: We studied 38 children diagnosed with JIA and 45 healthy children. We quantified GAAGs by assessing the concentration of unsaturated disaccharide units formed by digestion of isolated glycosaminoglycans with chondroitinase ABC, while COMP, YKL-40, and PDGF-BB were quantified using immunoenzymatic methods., Results: Compared to the control group, GAAGs and COMP levels were significantly lower, while YKL-40 levels were higher in the blood of patients with aggressive JIA, qualified for ETA treatment. ETA therapy leading to clinical improvement simultaneously promoted normalization of COMP and YKL-40 levels, but not GAAGs. After 24 months of taking ETA, glycan levels were still significantly lower, relative to controls. GAAGs, COMP, and YKL-40 levels were significantly influenced by ADAMTS4, ADAMTS5, and PDGF-BB levels both before and during ETA treatment., Conclusions: The dynamics of changes in marker concentrations during treatment seem to indicate that measurement of COMP and YKL-40 levels can be used to assess the chondroprotective biological efficacy of therapy. In contrast, changes in GAAGs concentrations reflect systemic extracellular matrix transformations in the course of JIA.

The near-edge X-ray absorption fine structure (NEXAFS) spectra of the gas-phase isoxazole molecule have been measured by collecting total ion yields at the C, N, and O K-edges. The spectral structures have been interpreted using time-dependent density functional theory (TD-DFT) with the short-range corrected SRC2-BLYP exchange-correlation functional. Experimental and calculated energies of core excitations are generally in good agreement, and the nature of observed core-excitation transitions has been elucidated. The experimental C 1s, N 1s, and O 1s core electron binding energies (CEBEs) have additionally been estimated from another yield measurement where the neutral fragments in high-Rydberg (HR) states were ionized by the electric field. For comparison, theoretical CEBEs have been calculated at the ΔM06-2X//mixed basis set level. We have also calculated the vibrationally resolved spectra pertaining to the lowest C 1s and N 1s core-excited roots in the Franck-Condon-Herzberg-Teller (FCHT) approximation. These spectra correlate well with the observed spectral features and have proven useful in resolving certain ambiguities in the assignment of the low-lying C 1s NEXAFS bands.

We assessed the effect of two-year etanercept (ETA) therapy on the metabolism of the cartilage extracellular matrix (ECM) in patients with juvenile idiopathic arthritis (JIA)., Methods: We performed a quantitative evaluation of glycosaminoglycans (GAGs) (performed by the multistage extraction and purification method) in blood obtained from patients before and during 24 months of ETA treatment, as potential biomarker of joint dysfunction and indicators of biological effectiveness of therapy. Since the metabolism of GAGs is related to the activity of proteolytic enzymes and prooxidant-antioxidant factors, we decided to evaluate the relationship between GAGs and the levels of metalloproteinases (MMP), i.e., MMP-1 and MMP-3 (using immunoenzymatic methods), as well as the total antioxidative status (TAS) (using the colorimetric method) in blood of the JIA patients., Results: When compared to the controls, GAGs and TAS concentrations were significantly lower in patients with an aggressive course of JIA qualified for ETA treatment. MMP-1 and MMP-3 levels were significantly higher versus control values. An anti-cytokine therapy leading to clinical improvement does not lead to the normalization of any of the assessed parameters. GAGs concentration is significantly related to MMP-1, MMP-3, TAS, TOS, and CRP levels., Conclusion: The results of the present study indicate the necessity of constant monitoring of the dynamics of destructive processes of articular cartilage in children with JIA. We suggest that GAGs may be a useful biomarker to assess the clinical status of the extracellular matrix of joints.

Albumin is one of the major components of synovial fluid. Due to its negative surface charge, it plays an essential role in many physiological processes, including the ability to form molecular complexes. In addition, glycosaminoglycans such as hyaluronic acid and chondroitin sulfate are crucial components of synovial fluid involved in the boundary lubrication regime. This study presents the influence of Na+, Mg2+ and Ca2+ ions on human serum albumin-hyaluronan/chondroitin-6-sulfate interactions examined using molecular docking followed by molecular dynamics simulations. We analyze chosen glycosaminoglycans binding by employing a conformational entropy approach. In addition, several protein-polymer complexes have been studied to check how the binding site and presence of ions influence affinity. The presence of divalent cations contributes to the decrease of conformational entropy near carboxyl and sulfate groups. This observation can indicate the higher affinity between glycosaminoglycans and albumin. Moreover, domains IIIA and IIIB of albumin have the highest affinity as those are two domains that show a positive net charge that allows for binding with negatively charged glycosaminoglycans. Finally, in discussion, we suggest some research path to find particular features that would carry information about the dynamics of the particular type of polymers or ions.

We assessed the effect of 24-month anti-tumor necrosis factor alpha (TNF-α) treatment on the remodeling of the cartilage extracellular matrix (ECM) in patients with juvenile idiopathic arthritis (JIA)., Methods: Quantitative evaluation of keratan sulfate (KS), hyaluronic acid (HA), hyaluronan and proteoglycan link protein 1 (HAPLN1), as potential biomarkers of joint dysfunction, and the levels of a disintegrin and metalloproteinase with thrombospondin motifs (ADAMTS) 4 and 5, total oxidative status (TOS) and transforming growth factor (TGF-β1) was performed (using immunoenzymatic methods) in blood obtained from patients before and after 24 months of etanercept (ETA) treatment., Results: When compared to the controls, KS, HA and HAPLN1 levels were significantly higher in patients with an aggressive course of JIA qualified for ETA treatment. An anti-cytokine therapy leading to clinical improvement promotes the normalization only of the HA level. Proteolytic and pro-oxidative factors, present in high concentrations in patients before the treatment, correlated with HAPLN1, but not with KS and HA levels. In these patients, negative correlations were found between the levels of TGF-β1 and KS, HA and HAPLN1., Conclusion: The anti-TNF-α therapy used in patients with JIA has a beneficial effect on ECM cartilage metabolism, but it does not completely regenerate it. The changes in the plasma HA level during the anti-cytokine therapy suggest its potential diagnostic utility in monitoring of disease activity and may be used to assess the efficacy of ETA treatment.

There is much evidence that the vertebrate lung originated from a progenitor structure which was present in bony fish. However, critical basic elements for the evolution of breathing in tetrapods, such as the central rhythm generator sensitive to CO 2 /pH and the pulmonary surfactant, were present in the lungless primitive vertebrate. This suggests that the evolution of air breathing in all vertebrates may have evolved through exaptations. It appears that the capability for proliferation of alveolar type 1 (AT1) cells is the "critical factor" which rendered possible the most radical subsequent innovation-the possibility of air breathing. "Epithelial remodeling," which consists in proliferation of alveolar cells-the structural basis for gas diffusion-observed in the alimentary tract of the gut-breathing fishes (GBF) has great potential for application in biomedical research. Such a process probably led to the gradual evolutionary development of lungs in terrestrial vertebrates. Research on the cellular and molecular mechanisms controlling proliferation of squamous epithelial cells in the GBF should contribute to explaining the regeneration-associated phenomena that occur in mammal lungs, and especially to the understanding of signal pathways which govern the process., (© 2022. The Author(s).)

A series of quaternary diammonium salts derivatives of 1,4:3,6-dianhydro-l-iditol were synthesized, using isommanide (1,4:3,6-dianhydro-d-mannitol) as a starting material. Both aromatic (pyridine, 4-( N , N -dimethylamino)pyridine (DMAP), (3-carboxamide)pyridine; N -methylimidazole) and aliphatic (trimethylamine, N , N -dimethylhexylamine, N , N -dimethyloctylamine, N , N -dimethyldecylamine) amines were used, giving eight gemini quaternary ammonium salts (QAS). All salts were tested for their antimicrobial activity against yeasts, Candida albicans and Candida glabrata , as well as bacterial Staphylococcus aureus and Escherichia coli reference strains. Moreover, antibacterial activity against 20 isolates of S. aureus collected from patients with skin and soft tissue infections ( n = 8) and strains derived from subclinical bovine mastitis milk samples ( n = 12) were evaluated. Two QAS with octyl and decyl residues exhibited antimicrobial activity, whereas those with two decyl residues proved to be the most active against the tested pathogens, with MIC of 16-32, 32, and 8 µg/mL for yeast, E. coli, and S. aureus reference and clinical strains, respectively. Only QAS with decyl residues proved to be cytotoxic in MTT assay against human keratinocytes (HaCaT), IC 50 12.8 ± 1.2 μg/mL. Ames test was used to assess the mutagenic potential of QAS, and none of them showed mutagenic activity in the concentration range 4-2000 µg/plate.

The interactions of ions with molecules and the determination of their dissociation patterns are challenging endeavors of fundamental importance for theoretical and experimental science. In particular, the investigations on bond-breaking and new bond-forming processes triggered by the ionic impact may shed light on the stellar wind interaction with interstellar media, ionic beam irradiations of the living cells, ion-track nanotechnology, radiation hardness analysis of materials, and focused ion beam etching, deposition, and lithography. Due to its vital role in the natural environment, the pyridine molecule has become the subject of both basic and applied research in recent years. Therefore, dissociation of the gas phase pyridine (C 5 H 5 N) into neutral excited atomic and molecular fragments following protons (H + ) and dihydrogen cations (H 2 + ) impact has been investigated experimentally in the 5-1000 eV energy range. The collision-induced emission spectroscopy has been exploited to detect luminescence in the wavelength range from 190 to 520 nm at the different kinetic energies of both cations. High-resolution optical fragmentation spectra reveal emission bands due to the CH(A 2 Δ→X 2 Π r ; B 2 Σ + →X 2 Π r ; C 2 Σ + →X 2 Π r ) and CN(B 2 Σ + →X 2 Σ + ) transitions as well as atomic H and C lines. Their spectral line shapes and qualitative band intensities are examined in detail. The analysis shows that the H 2 + irradiation enhances pyridine ring fragmentation and creates various fragments more pronounced than H + cations. The plausible collisional processes and fragmentation pathways leading to the identified products are discussed and compared with the latest results obtained in cation-induced fragmentation of pyridine.

This paper seeks to examine how the Mn-Co spinel interconnect coating microstructure can influence Cr contamination in an oxygen electrode of intermediate temperature solid oxide cells, at an operating temperature of 750 °C. A Mn-Co spinel coating is processed on Crofer 22 APU substrates by electrophoretic deposition, and subsequently sintered, following both the one-step and two-step sintering, in order to obtain significantly different densification levels. The electrochemical characterization is performed on anode-supported cells with an LSCF cathode. The cells were aged prior to the electrochemical characterization in contact with the spinel-coated Crofer 22 APU at 750 °C for 250 h. Current-voltage and impedance spectra of the cells were measured after the exposure with the interconnect. Post-mortem analysis of the interconnect and the cell was carried out, in order to assess the Cr retention capability of coatings with different microstructures.

The principal objective of the study was the isolation and identification of bacteria that are present in mature bee bread (BB) and dried (ready for selling and consumption) bee pollen (BP). Obtained isolates were screened for their potential to inhibit select human pathogenic bacteria and their ability to produce enzymes of particular industrial importance. Four and five samples of BP and BB, respectively, were used for the study. In total, 81 strains of bacteria were isolated, and 34 (42%) of them exhibited antagonistic interactions with at least one reference strain of pathogenic bacteria, namely Staphylococcus aureus ATCC 25923, Staphylococcus aureus ATCC 29213, Staphylococcus epidermidis 12228, Pseudomonas aeruginosa ATCC 27857, and Escherichia coli ATCC 25922. The sequencing of the 16S rRNA gene revealed that all strains producing antimicrobials belong to the genus Bacillus spp., and among them, five species were identified: B. pumilus ( n = 17), B. altitudinis ( n = 9), B. licheniformis ( n = 4), B. subtilis ( n = 2), and B. safensis ( n = 1). Furthermore, 69, 54, 39, and 29 of the strains exhibited lipolytic, proteolytic, cellulolytic, and esterolytic activity, respectively. Alpha amylase and beta galactosidase activity were rarely observed, and none of the strains produced laccase. The outcomes of the study revealed that BP and BB can be considered potential sources of bacteria producing antimicrobial agents and/or enzymes of particular industrial importance. Of course, additional research is required to verify this hypothesis, but the results of preliminary studies are promising.

Some oxygen defective fluorites are non-Newnham electrostrictors, i.e., the electromechanical response does not depend on their dielectric properties. Here, we show gigantic electrostriction in nanocrystalline 25 mol% praseodymium doped ceria (PCO) bulk ceramics. The material was fabricated with a field-assisted spark plasma sintering (SPS) process from high-purity nanoscale PCO powders (<20 nm). The SPS process consolidates the powders into a single-phase, highly dense material with a homogeneous microstructure and large grain boundary extension. Various thermally and chemically stable ionic defects are incorporated into the nanostructure, leading to superior electrical conductivity. The material shows an electrostriction strain coefficient (M33) of ∼10-16 m2 V-2 at frequencies below 100 Hz at room temperature. Such performance is comparable and even superior to Newnham's electrostrictors, such as ferroelectric ceramics and polymeric actuators. Comparative analysis with polycrystals suggests that nanostructured PCO possesses electromechanically active nanodomains of Pr3+-VO pairs. Such results are unexpected and open novel insights on non-Newnham electrostrictors.

The present investigation aimed to assess the combinational effect of commonly used antipyretics and antiseptics with ethanolic extracts of propolis (EEPs) on the growth inhibition of Staphylococcus aureus . The broth microdilution checkerboard assay revealed synergistic interactions between all investigated antipyretics, namely acetylsalicylic acid, ibuprofen, and acetaminophen, with EEPs samples. The values of the fractional inhibitory concentration (ΣFIC) index for all these combinations were <0.5. While, in the case of considered antiseptics, namely chlorhexidine, octenidine dihydrochloride, and 2-phenoxyethanol, the positive interaction was confirmed only for the last one (values of ΣFIC in the range 0.0625-0.25). Combinations of two other agents with all four samples of EEPs resulted in an important antagonistic effect (values of ΣFIC ≥ 4.5). Propolis is mostly dedicated to the treatment of skin/wound infections; thus, these findings are of particular practical importance. The outcomes of the study also support the hypothesis that the propolis's antimicrobial effect is due to the combined (synergistic) action of several ingredients rather than the presence of one component of high antibacterial activity. The composition of 13 ingredients of EEPs (at a concentration below the MIC (minimum inhibitory concentration) of the most active agent) exhibited considerably high anti-staphylococcal efficiency with MIC = 128 µg/mL.

This study aimed at investigation of the antimicrobial potential of ethanolic extracts of bee bread (BB) and bee pollen (BP) and suspensions of these products in MHB (Mueller Hinton Broth). We covered 30 samples of BP and 19 samples of BB harvested in Polish apiaries. Slightly lower activity was observed against Gram-negative bacteria compared to Gram-positive staphylococci. BB extracts exhibited higher inhibitory potential with minimum inhibitory concentration (MIC) values in the range from 2.5 to 10% ( v / v ) against Staphylococcus aureus ATCC 25923 and ATCC 29213. Most active BB extracts, namely, BB6, BB11 and BB19, effectively inhibited growth of clinical isolates of S. aureus ( n = 9), including MRSA ( methicillin resistant Staphylococcus aureus ) strains ( n = 3) at concentrations ranging from 2.5 to 5.0% ( v / v ). Minimal bactericidal concentration (MBC) values were in the same range of concentrations; however, a shift from 2.5 to 5.0% ( v / v ) was observed for some products. The most active BP extracts inhibited the growth of reference strains of S. aureus at a concentration of 5% ( v / v ). Up to the concentration of 20% ( v / v ) three and seven BP extracts were not able to inhibit the growth of S. aureus ATCC 29213 and S. aureus ATCC 25923 respectively. The growth of staphylococci was also importantly inhibited in suspensions of the products in MHB. No correlation between phenolic content and antimicrobial activity was observed.