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.

Alkaloid-based urea derivatives were produced with high yield through the reaction of anabasine and cytisine with isoxazolylphenylcarbamates in boiling benzene. Their antitumor ac-tivity in combination with the commonly used six anticancer drugs namely cyclophosphane, fluorouracil, etoposide, cysplatine, ribomustine with different mechanisms of action was investi-gated. Based on the quantum chemical calculations data and molecular docking, hypotheses have been put forward to explain their mutual influence when affecting on the С6 rat glioma model cells.

The new hybrid composite materials for PEM fuel cell were synthesized by UV-polymerization of acrylic monomers (acrylonitrile (AN), acrylic acid (AA), ethylene glycol dimethacrylate (EGDMA)) and sulfo aromatic monomer – sodium styrene sulfonate (SSS), and tetraethoxysilane/3-methacryloxypropyltrimethoxysilane (TEOS/MAPTMS)-based sol-gel system. By means of X-ray spectroscopy fractal structure of the obtained materials was characterized. Proton conductivity and viscoelastic properties of the materials were investigated depending on the content of inorganic component in nanocomposites. On the basis of impedance studies, an equivalent scheme is proposed that successfully describes the proton conductivity in the synthesized composite electrolyte membranes.

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.

The reaction of 2-((diphenylmethylene)amino)acetonitrile with (E)-1-phenyl-3-(thiophen-2-yl)prop-2-en-1-one was performed by using 33% NaOH in CH3CN for 30 min at 0°C. The main product - rel-(2R,3S)-2-((diphenylmethylene)amino)-5-oxo-5-phenyl-3-(thiophen-2-yl)pentanenitrile was isolated and characterized by IR, 1H NMR, 13C NMR and high-resolution mass spectrometry (HRMS).

Indole is a versatile pharmacophore widely distributed in bioactive natural products. This privileged scaffold has been found in a variety of molecules isolated from marine organisms such as algae and sponges. Among these, indole alkaloids represent one of the biggest, most promising family of compounds, having shown a wide range of pharmacological properties, including anti-inflammatory, antiviral and anticancer activities. The aim of this review is to show the current scenario of marine indole alkaloid derivatives, covering not only the most common chemical structures, but also new synthetic routes developed during the last years as well as promising therapeutic applications.

This study presents the development of a diglycidyl monomer containing two imine groups that can act as dynamic and reversible bonds. During the curing of the monomer with two different amine hardeners, we confirmed the formation of new imine groups due to the transamination reaction, not reported before, between the imine groups of the diepoxy monomer with the amine groups of the hardener. The effect of this structural change is observed for the first time in the stress relaxation behavior, resulting in the overlapping of two different relaxation modes. The analytical modelling could extract two distinct characteristic relaxation times using a double-element Maxwell model. A second characterization of the stress relaxation process by frequency sweep experiments was performed to corroborate the results obtained, confirming speedy stress relaxation. Acid-catalyzed hydrolysis was performed on the studied materials, demonstrating the complete degradation of the network. We finally confirmed that the synthesized diepoxy compound is suitable for preparing carbon fiber-reinforced composite materials, demonstrating easy fiber impregnation, fast reshaping and especially a total degradation of the polymer matrix that allows the recovery of the carbon fibers in mild conditions. This epoxy-amine system is an excellent candidate for overcoming the traditional limits of thermosets in preparing fiber-reinforced composites.

The study of biologically active substances from natural sources shows the prospect of obtaining a new type of antimicrobial agents, highly effective against pathogenic microorganisms and non-toxic to humans. Our study reveals for the first time that Cornu aspersum mucus has the potential to act as a source of antibacterial agents against bacterial pathogens such as Bacillus cereus 1085, Propionibacterium acnes 1897, Salmonella enterica 8691, Enterococcus faecalis 3915, and Enterococcus faecium 8754. Both mucus fractions with MW<20 kDa and MW>20 kDa showed antimicrobial activity and antioxidant properties that’s why they can be turned into an alternative agent to expensive synthetic antibacterial compounds. Using de novo sequencing 16 novel peptides with potential antibacterial activity were identified by in a fraction with MW<20 kDa. The results of electrophoretic and proteomic analysis of mucus fraction with MW >20 kDa presented proteins with potential antibacterial activity highly homologous to hemocyanins, mucus protein Aspernin, lectins, L-amino acid oxidase-like protein, and mucins (mucin-5AC, mucin-5B, mucin-2 and mucin-17). Thanks to the synergistic action of the bioactive components, the mucus fraction with MW > 20 kDa in low concentrations per 8–2 µg/mL showed promising antimicrobial activity against the tested bacteria, comparable to Vancomycin and without unwanted cytotoxic effects against non-target cells. Additionally, C. aspersum mucus fractions were found to have a positive effect on eukaryotic organisms by reducing the levels of intracellular oxidative damage and increasing the antioxidant capacity of the cell. These findings could serve as a basis for the development of a potent non-cytotoxic antibacterial agent to replace conventional antibiotics and avoid the development of antibiotic resistance.

The corrosion behavior of the TiTaNbZrAg alloys with different amounts of Tantalum (0 %, 10 % and 20%) and with distinct surface topography (smooth and rough) was investigated in phosphate buffer solution (PBS) for long-time immersion (1000 hours). The corrosion resistance was studied by Open circuit potential (OCP), potentiodynamic polarization (PP) and electrochemical impedance spectroscopy (EIS). From the potentiodynamic investigations, it was observed that all types of samples show good corrosion resistance (i.e. Rcorr < 10µm y-1) and may be used successfully for medical applications. However, the samples with smooth surface and with a certain amount of Ta (10 % and 20%) exhibit the best corrosion performance (Rcorr < 1µm y-1). As regard the samples with rough surface, the results evidenced that they show lower corrosion resistance (1< Rcorr < 3 µm y-1), suggesting that the Ta presence not necessary brings about a very good corrosion protection. Actually, the synergetic effect of both the presence of Ta and surface roughness plays an important role in corrosion behavior. Based on literature reports, we assume that the good corrosion resistance results from the good stability of the film, formed mainly from Ta2O5 and TiO2, formed on the alloy surface during immersion in PBS.

Polymeric Intraocular lenses (IOLs) are vital for restoring vision following cataract surgery and for correcting refractive errors. Despite technological and medical advancements, challenges persist in achieving optimal vision and preventing complications. Surface modifications aim to mitigate the risk of posterior capsule opacification (PCO), while pre-operative measurements aid in selecting suitable IOLs. However, individualized solutions are lacking and there is a clear demand for the development of fully customised IOL surfaces. We employ laser micromachining technology for precise modifications via ablation on PMMA and Acrylic IOLs, using femtosecond (fs), nanosecond (ns), and diode continuous wave (CW) lasers, at wavelengths ranging from near-ultraviolet to infrared. Characterization reveals controlled ablation patterning, achieving feature sizes from as small as 400 nm to several micrometers. Regular and confocal Micro-Raman spectroscopy revealed alterations of the IOL materials' structural integrity for some pattering cases, thus affecting the optical properties, while these can be minimised by proper selection of micromachining conditions. The results suggest the feasibility of accurate IOL patterning, which could offer personalized vision correction solutions, based on relevant corneal wavefront data, thus surpassing standard lenses, marking a significant advancement in cataract surgery outcomes.

The targeted compounds in this research, resveratrol analogs 1–14 were synthesized as mixtures of isomers by the Wittig reaction using heterocyclic triphenylphosphonium salts and various benzaldehydes. The planned compounds were those possessing the trans-configuration as the biologically active trans-resveratrol. The pure isomers were obtained by repeated column chromatography in various isolated yields depending on the heteroaromatic ring. It was found that butyrylcholinesterase (BChE) was more sensitive to the heteroaromatic resveratrol analogs than acetylcholinesterase (AChE), except for 6, the methylated thiophene derivative with chlorine, which showed equal inhibition toward both enzymes. Compounds 5 and 8 achieved the highest BChE inhibition with IC50 values of 22.9 and 24.8 μM, respectively. The same as with AChE and BChE, methylated thiophene subunits of resveratrol analogs showed better enzyme inhibition than unmethylated ones. Two antioxidant spectrophotometric methods, DPPH and CUPRAC, were applied to determine the antioxidant potential of new heteroaromatic resveratrol analogs. Molecular docking of these compounds was conducted to visualize the ligand-active site complexes' structure and identify the non-covalent interactions responsible for the complex's stability, which influence the inhibitory potential. As ADME properties are crucial in developing drug product formulations, they have also been addressed in this work. The potential genotoxicity is evaluated by in silico studies for all compounds synthesized.

An extensive thermodynamic study of N-methylformamide (CAS RN: 123-39-7) and N,N-dimethylformamide (CAS RN: 68-12-2), is presented in this work. The liquid heat capacities of N-methylformamide were measured by Tian–Calvet calorimetry in the temperature interval (250 – 300) K. The vapor pressures for N-methylformamide and N,N-dimethylformamide were measured using static method in the temperature range 238 K to 308 K. The ideal-gas thermo-dynamic properties were calculated using a combination of the density functional theory (DFT) and statistical thermodynamics. A consistent thermodynamic description was developed using the method of simultaneous correlation, where the experimental and selected titerature data for vapor pressures, vaporization enthalpies, and liquid phase heat capacities and calculated ide-al-gas heat capacities are treated together to ensure overall thermodynamic consistency of the results. Resulting vapor pressure equation is valid from the triple point to the normal boiling point temperature.

Xanthone derivatives, a class of natural compounds abundantly found in plants such as mangosteen (Garcinia mangostana) and certain herbs, have garnered substantial interest due to their diverse pharmacological properties, including antioxidant, anti-inflammatory, and anti-cancer activities. Recent investigations have unveiled their potential as modulators of enzymatic activity, prompting exploration into their effects on hyaluronidase-mediated HA degradation, and their effects in topical treatment of telangiectasia and rosacea. Telangiectasia and rosacea are common dermatological conditions characterized by chronic skin inflammation, vascular abnormalities, and visible blood vessels, resulting in significant cosmetic concerns and impaired quality of life for affected individuals. This review aims to provide a comprehensive overview of the current understanding regarding the interplay between mechanisms of action by which xanthone derivatives exert their therapeutic effects, including the inhibition of pro-inflammatory cytokines, modulation of oxidative stress pathways, and regulation of vascular endothelial growth factors. Furthermore, we will discuss the implications of harnessing xanthone derivatives as therapeutic agents for mitigating vascular dysfunction and its associated pathologies, thereby offering insights into future research directions and therapeutic strategies in the field of vascular biology.

The growing interest in benchtop NMR systems is visible in a vast number of applications in science and industry. Low-field nuclear magnetic resonance (LF-NMR) became an instant in technologies that productions are dependent on the reliable structure identification, grade and purity control, chemical process inspection or reaction monitoring. Beyond the benefits of being cost-, space-, maintenance- and user friendly, insufficient sensitivity and low signal resolution are the main drawbacks, due to which the low-field NMR (LF-NMR) in the fields of organic chemistry and synthesis remains limited to solely academic teaching purposes. Herein, we discuss the possibilities of LF-NMR for the needs of organic chemistry and synthesis on a set of compounds 1-4 achieved as the products of student’s laboratory course and organic derivatives 5-8 that are from our research interests. Chemical structure determination of all compounds 1-8 presented herein was performed using the benchtop-type NMR instrument operating at 60 MHz (Pulsar Oxford Ltd.). Structure of novel compounds 5-7 prepared under the aims of our research was characterized by combined 1H/19LF-NMR and compared with an appropriate high-field NMR data from Bruker Ascend Instrument (400 MHz). Finally, possibilities of the low-field NMR as an analytical tool for the research purposes in the fields of organic chemistry and synthesis are documented on a set of 1H and 2D 1H-1H COSY for azomethine 8.

For centuries, humans have relied on natural products to prevent and treat numerous health issues. However, biologically active compounds from natural sources, such as polyphenols, face significant challenges, including low solubility, rapid metabolism, and instability, which hinder their effectiveness. Advances in science and nanotechnology have provided solutions to overcoming these problems through the use of porous silica materials. These materials possess unique properties, such as a high specific surface area, adjustable particle and pore sizes, and a surface that can be easily and selectively modified. In this review, we summarize and discuss findings on how the pore and particle size, structure, and surface modification of silica materials influence the preparation of efficient delivery systems for biologically active polyphenols from natural sources. The available data demonstrate how parameters such as adsorption capacity, release and antioxidant properties, bioavailability, solubility, stability, etc. of the studied delivery systems could be affected by the structural and chemical characteristics of the porous silica carriers.

Self-healing materials research spans many academic disciplines and employs a wide range of methodologies. Some of the developed concepts are driven by the direct application of the materials. However, a deeper understanding of the basic mechanisms and principles of self-healing materials is still a challenging aim. Nature has mostly served as an inspiration for the development of new self-healing materials, and it will undoubtedly continue to be a significant source of inspiration for the creation of novel ideas. This review encompasses the principles of self-healing mechanisms based on the concepts of autonomous and non-autonomous procedures. Studies based on smart composite materials with autonomous self-healing properties are also included and discussed from two aspects of intrinsic or extrinsic abilities, taking into consideration their components and structures as well as the design of these composites. Finally, special attention is given to the application of the materials in several fields such as aerospace, automotive, marine, energy, medical and healthcare, military, and construction.

Hydrogen gas (H2) has attracted attention as a next-generation clean energy source. Its efficient and safe preparation and utilization are crucial in both industry and organic chemistry. In this study, a Pt/CB-catalyzed MW-mediated continuous-flow hydrogenation reaction was developed using methylcyclohexane (MCH) as the reducing agent (hydrogen carrier). Alkynes, alkenes, nitro groups, benzyl esters, and aromatic chlorides were chemoselectively hydrogenated using Pt/CB under MW-assisted continuous-flow conditions. This methodology represents a safe and energy-efficient hydrogenation process, as it eliminates the need for an external hydrogen gas supply or heating jackets as a heat medium. Further application of MW-mediated continuous-flow hydrogenation reactions is a viable method for the efficient generation and utilization of sustainable energy.

The chemical investigation of the anti-yeast methanol extract from the stem bark of Terminalia mantaly led to the isolation of seven compounds: 3-O-methyl-4-O-α-rhamnopyranoside ellagic acid (1), 3-O-mehylellagic acid (2), arjungenin or 2,3,19,23-tetrahydroxyolean-12-en-28-oïc acid (3), arjunglucoside or 2,3,19,23-tetrahydroxyolean-12-en-28-oïc acid glucopyranoside (4), 2α,3α,24-trihydroxyolean-11,13(18)-dien-28-oïc acid (5), stigmasterol (6), stigmasterol 3-O-β-D-glucopyranoside (7). Their structures were established by means of spectroscopic analysis and comparison with published data. Compounds 1-5 were tested in vitro for activity against three pathogenic yeast isolates, Candida albicans, Candida parapsilosis and Candida krusei. The activity of compounds 1, 2 and 4 were comparable to that of the reference compound fluconazole (MIC values below 32 µg/ml) against the three tested yeast isolates. They were also tested for inhibitory properties against four enzymes of metabolic significance: Glucose-6-Phosphate Deshydrogenase (G6PD), human erythrocyte Carbonic anhydrase I and II (hCA I and hCA II), Glutathione S-transferase (GST). Compound 4 showed highly potent inhibitory property against the four tested enzymes with overall IC₅₀ values below 4 µM and inhibitory constant (Ki) <3 µM.

The bimetallic (Ta/(Ti, V, Co, Nb) mesoporous MCM-41 nanoparticles were obtained by direct synthesis and hydrothermal treatment. The obtained mesoporous materials were characterized by XRD, XRF, N2 adsorption/desorption, SEM, TEM, XPS, Raman, UV-Vis, PL spectroscopy. A more significant effect was observed on mesoporous structure, typi-cally for MCM-41, and optic properties if the second metal (Ti, Co) does not belong to the same Vb group with Ta as V, Nb. The obtained new nanoparticles were used as catalysts for oxidation with H2O2 of olefinic compounds (1,4 cyclohexadiene, cyclohexene, styrene) and photodegradation of organic pollutants (phenol, methyl orange) from water. The re-sults showed improving of activity and selectivity in oxidation reactions by addition of the second metal to Ta-MCM-41 catalyst. The slow addition of H2O2 was also be benefit for the selectivity in epoxide products and stability of the catalysts. The band gap energy values decrease in the presence of the second metal and the band edge diagram evidenced posi-tive potential for all the conduction band of the bimetallic samples except TaTi-MCM-41. The higher photocatalytic degradation was obtained for samples with TaTi and TaV.

Leishmaniasis are neglected diseases that affect regions such as South Asia, South Africa and Latin America, less developed regions. Current treatment, for cutaneous, mucocutaneous and visceral leishmaniosis, which are the main forms of the disease, is based on the administration of pentavalent antimonial and amphotericin B. However, these drugs have low efficacy and high toxicity. For this reason, the search for new treatments for this disease is necessary, based on studies of new molecules and their conformations. The research proposed the conformational study of brominated guanidine compounds with potential antileishmanial activity using Nuclear Magnetic Resonance (NMR) and X-ray diffraction (XRD) techniques. The present study involves the bro-minated molecules, LQOF-G2, LQOF-G30, LQOF-G35 and LQOF-G35-Br. The later was synthesized by the reaction of LQOF-G35 with NBS under IR irradiation at 120 Watts of potency and dichloro-methane as solvent by 12-h of exposition. The obtained results demonstrated the efficiency of the bromination method, since two bromines atoms entered the molecule. Furthermore, NMR analysis showed the occurrence of a conformational change from Z to E when compound LQOF-G35 was brominated to LQOF-G35-Br. This feature was well confirmed by comparative DRX study of the LQOF-G35 and LQOF-G35-Br compounds. The antileishmanial activity of LQOF-G2 e LQOF-G35 motivated the synthesis of new brominated compounds LQOF-G30 e LQOF-G35-Br.

The critical role of global electron density transfer (GEDT) in increasing the reaction rate of polar organic reactions has been studied within the framework of Molecular Electron Density Theory (MEDT). To this end, the series of the polar Diels-Alder (P-DA) reactions of cyclopentadiene with cyanoethylene derivatives, for which experimental kinetic data are available, have been chosen. A complete linear correlation between the computed activation Gibbs free energies and the GEDT taking place at the polar transition state structures (TSs) is found; the higher the GEDT at the TS, the lower the activation Gibbs free energy. An interacting quantum atoms (IQA) energy partitioning analysis allows establishing a complete linear correlation between the electronic stabilization of the electrophilic ethylene frameworks and the GEDT taking place at the polar TSs. This finding supports Parr’s proposal for the definition of the electrophilicity  index (J. Am. Chem. Soc., 1999, 121, 1922). The present MEDT study allows establishing the critical role of the GEDT in the acceleration of polar reactions, since the electronic stabilization of the electrophilic framework with the electron density gain is greater than the destabilization of the nucleophilic one, making a net favorable electronic contribution to the decrease of the activation energy.

Japanese plum tree (Prunus salicina Lindl.) is mainly cultivated in temperate areas of China and some European countries. Certain amounts of wood (from pruning works) are generated every year from this crop of worldwide commercial significance. The main objective of this work was to value this agricultural woody residue, for which the chemical composition of pruning wood extracts from six Japanese plum cultivars was investigated, and the antiproliferative activity of extracts and pure phenolics present in those extracts was measured. For the chemical characterization, total phenolic content and DPPH radical-scavenging assays and HPLC‒DAD/ESI‒MS analyses were performed, the procyanidin (‒)-ent-epicatechin-(2α→O→7,4α→8)-epicatechin (5) and the propelargonidin (+)-epiafzelechin-(2β→O→7,4β→8)-epicatechin (7) being the major components of the wood extracts. Some quantitative differences were found among plum cultivars, and the content of proanthocyanidins ranged from 1.50 (cv. ‘Fortune’) to 4.44 (cv. ‘Showtime’) mg/g of dry wood. Regarding the antitumoral activiy, eight wood extracts and four phenolic compounds were evaluated in MCF-7 cells after 48 h of induction, showing the wood extract from cv. ‘Songold’ and (‒)-annphenone (3) the best antiproliferative activity (IC50: 424 ppm and 405 ppm, respectively).

The reaction of berberine derivatives containing at O-9 position N,N-disubstituted acetamide fragments with sodium borohydride in methanol at 0 °C leads to a mild reduction of the "C" cycle with the formation of corresponding tetrahydroberberine derivatives with moderate to good yields.

In this research the efficiency of degradation of different organic contaminant classes, including pesticides (tembotrione, clomazone), pharmaceuticals (ciprofloxacin, 17α-ethinyl estradiol) and mycotoxins (zearalenone, deoxynivalenol, fumonisin B1), by subcritical water treatment, was studied in model systems. All experiments were conducted in a house-made batch type pilot reactor. The research was focused on the optimization of the treatment parameters by using moderate treatment conditions. Optimization of the remediation processes of water contaminated with 17α-ethinyl estradiol, tembotrione, clomazone, ciprofloxacin, was conducted by testing different homogeneous and heterogeneous catalysts, as well as different gas atmospheres (nitrogen and carbon-dioxide) for pressurization of the process system. Mycotoxins in water were degraded without catalysts and all experiments were conducted in nitrogen atmosphere. Optimization was conducted by defining the optimal combination of the treatment temperature and time, oriented towards energy saving and minimization of the technical requirements. The degradation efficiency in all tested samples was determined by HPLC analysis.

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

During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF) unit by a -conjugated bridge (1). Interestingly, this system behaves as a semiconductor with high conductivity and small energy gap under high pressure. With the aim of developing a new material with improved conducting properties, we have designed and synthesized the radical dyad 2 which was functionalized with an ethylenedithio (EDT) group in order to improve the intermolecular interactions of the TTF subunits. The physical properties of the new radical dyad 2 were studied in detail in solution to further analyze its electronic structure as well as its potential use as radical conductor in the solid state.

In the frame of our diversity-oriented research on multitarget small molecule anticancer agents, utilizing convergent synthetic sequences terminated by Sonogashira coupling reactions, a preliminary selection of representative alkyne-tethered vindoline hybrids was synthesized. The novel hybrids with additional pharmacophoric fragments of well-documented anticancer agents, including FDA-approved tyrosine-kinase inhibitors (imatinib and erlotinib) or ferrocene or chalcone units, were evaluated for their antiproliferative activity on malignant cell lines MDA-MB-231 (triple negative breast cancer), A2780 (ovarian cancer), HeLa (human cervical cancer) and SH-SY5Y (neuroblastoma) as well as human embryonal lung fibroblast MRC-5 served as reference non-malignant cell line for the assessment of the therapeutic window of the tested hybrids. The biological assays identified a trimethoxyphenyl-containing chalcone-vindoline hybrid (36) as a promising lead compound exhibiting submicromolar activity on A2780 cells with a marked therapeutic window. These results suggest that ovarian cancer might be considered as a prioritized target of treatment with 36.

New dimers of selected dipyridothiazines with an m-xylene linker have been designed, synthesized and characterized. Their structure was identified using 1H and 13C NMR as well as 2D NMR techniques (COSY, ROESY, HSQC and HMBC experiments) and HR MS spectrometry. The compounds were subjected to preliminary in silico biological profile tests using the Way2Drug server and analysis of the probable cytotoxic effect on various cancer cell lines. Preliminary in vitro cytotoxicity tests were performed against normal cell lines (HaCaT) and five cancer cell lines (SW480, SW620, MDA-MB-231, A-549, LN-229) showing moderate activity. An analysis of the structure-activity relationship was performed.

The concept of intelligence has many applications, such as coatings and cyber security. Smart coatings have the ability to sense and/or response to external stimuli and generally interact with their environment. Self-healing coatings represent a significant advance in improving material durability and performance using microcapsules and nanocontainers loaded with self-healing agents, catalysts, corrosion inhibitors, and water-repellents. These smart coatings can repair damage on their own and restore mechanical properties without external intervention and are inspired by biological systems. Properties that are affected by either momentary or continuous external stimuli in smart coatings can be related to corrosion, fouling, fungal, self-healing, pie-zoelectric, microbiological, etc. These coating properties can be obtained via combinations of either organic or inorganic polymer phases, additives and pigments. In this article, a review on the advancements of micro/nanocapsules for self-healing coatings is reported from the aspect of ex-trinsic self-healing ability. The concept of extrinsic self-healing coatings is based on the use of capsules or multichannel vascular systems loaded with healing agents/inhibitors. The outcome is that self-healing coatings exhibit improved properties compared to traditional coatings. It is mentioned that self-healing anticorrosive coating not only has enhanced passive barrier function, but also realizes active defense. As a result, there is a significant improvement of the service life and overall performance of the coating. Future research should be devoted to refining self-healing mechanisms and developing cost-effective solutions for a wide range of industrial applications.

1,3,5-Tris-(α-naphthyl)benzene is an organic non-electrolyte with notable stability of an amorphous phase. Its glassy and supercooled liquid states were previously studied by spectroscopic and calorimetric methods. However, the thermodynamic parameters of phase transitions available from the literature are inconsistent. In this work, the heat capacities of crystalline and liquid phases, the temperature dependence of the saturated vapor pressures, fusion and vaporization enthalpies were determined using differential and fast scanning calorimetry and verified using the estimates based on solution calorimetry. The structural features of 1,3,5-tris-(α-naphthyl)benzene are discussed based on the computations performed and the data on the molecular refractivity. The consistency between the values obtained by independent techniques was demonstrated. The deviations in the previously published data were attributed to possible polymorphism.

Oxidation of a mixture of nonlabelled (14N2H4) and 15N labeled (15N2H4) hydrazine in aqueous solutions produces 14N15N molecules, indicating the intermediate existence of N4H6 or N4H4 dimers with subsequent transfers of H atoms and splitting of lateral N-N bonds. To explain the key part of hydrazine oxidation reaction, the structures, thermodynamics, and electron characteristics of N4H4 molecules in aqueous solution are investigated at CCSD/cc-pVTZ level of theory. We have not found any spontaneous splitting of the bond between lateral nitrogen atoms in tetrazenes N4H4 during geometry optimization. The most probable N4H4 oxidation products are H2N-NH2 and N2, which are obtained by splitting the bond between central nitrogen atoms and so only 15N2 and 14N2 molecules are formed. Additionally, the formation of H3N-NH and N2 oxidation products is also preferred to structures without any N-N fissions. The formation of H2N=N and HN=NH reaction products is energetically less advantageous. Cyclo-N4H4 structures are stable, without any N-N fissions, but their very high Gibbs energies indicate their vanishing abundance in aqueous solution, so their involvement in hydrazine oxidation is highly improbable. Hydrazine oxidation to 14N15N molecules cannot be explained by tetrazene N4H4 intermediates.

The primary objective of this study was to identify a rapid and noninvasive methodology for effectively differentiating various herbal species cultivated in Eastern Poland. Typically, a plant's chemical profile is obtained using chromatographic methods; however, spectroscopic methods can serve as a complementary or independent tool for determining similarities in the analyzed samples. The investigation centered on leaves of plant species from the Lamiaceae family, encompassing basil, lavender, oregano, sage, and thyme. UV-VIS and ATR-FTIR spectra of dried plant samples' powder were recorded and subsequently analyzed using chemometric tools. This paper assesses the relative performance of different discrimination methods, including both traditional methods based on machine learning and those dealing with specimens associated with a specific category. Among the methodologies tested, SIMCA showed the best performance, particularly effective for small training sets.

Greek roots: "phos" (φῶς) - means "light" and "dynamis" (δύναμις) - means "force" or "power". Photodynamic therapy (PDT) is an innovative treatment method based on the ability of photosensitizers to produce reactive oxygen species after exposure to light of a specific wavelength range, either in the visible or near infrared range. This process results in damage to pathological cells, such as cancer cells, while minimizing the impact on healthy tissues. PDT is a promising direction in the treatment of many diseases, with particular emphasis on the fight against cancer and other diseases asso-ciated with excessive cell growth. The power of light contributed to the creation of phototherapy, whose history dates back to ancient times. It was then noticed that some substances exposed to the sun have a negative effect on the body, while others have a therapeutic effect. This work provides a detailed review of photodynamic therapy, from its origins to the present day. It is surprising how a seemingly simple beam of light can have such a powerful healing effect, which is used not only in dermatology, but also in oncology, surgery, microbiology, virology, and even dentistry. However, despite promising re-sults, photodynamic therapy still faces many challenges. The availability of this thera-py is limited due to the small number of centers offering this type of treatment and the high costs, which may be unaffordable for many patients. Moreover, photodynamic therapy requires further research and improvement.

The application potential of cellulosic materials in natural composites and other fields needs to be explored to develop innovative, sustainable, lightweight, functional biomass materials that are also environmentally friendly. This study investigated Typha augostifolia (Typha sp.) as a potential new raw material for extracting cellulose nanocrystals (CNCs) for application in wastewater treatment composites. Alkaline treatments and bleaching were used to remove cellulose from the stem fibers. The CNCs were then isolated from the recovered cellulose using acid hydrolysis. The study showed a few distinct functional groups (O-H, -C-H, =C-H and C-O, and C-O-C) in the Fourier Transform Infrared (FTIR) spectra. Scanning electron microscope (SEM) revealed the smooth surface of CPC and CNCs that resulted from removing lignin and hemicellulose from powdered Typha augostifolia. Based on the crystalline index, the powdered Typha augostifolia, CPC, and CNCs were 42.86%, 66.94% and 77.41%. The loss of the amorphous section of the Typha sp. fiber resulted in a decrease in particle size. It may be inferred from the features of a Typha sp. CNC that CNCs may be employed as reinforcement in composites for wastewater treatment.

Adhesive-invasive E. coli have been suggested to be associated with the development of Crohn's disease (CD). It is assumed that they can provoke the onset of the inflammatory process as a result of the invasion of intestinal epithelial cells, and then, due to survival inside macrophages, stimulate chronic inflammation and the development of granuloma. In previous reports, we have shown that passage of the СD isolate ZvL2 on minimal medium M9 supplemented with sodium propionate (PA) as a carbon source stimulates, and with glucose - inhibits the adherent-invasive properties and the ability to survive in macrophages. This effect was reversible and not observed for the laboratory strain K12 MG1655. We were able to compare the isogenic strain AIEС in two phenotypes - virulent (ZvL2-PA) and non-virulent (ZvL2-GLU). We showed that, unlike ZvL2-GLU, the ZvL2-PA activates the production of ROS and cytokines when interacting with neutrophils. The laboratory strain does not cause a similar effect. Differences in neutrophil NADH-oxidase activation and ζ potential for ZvL2-GLU and ZvL2-PA are associated with changes in the abundance of membrane proteins. Using differential 2D electrophoresis and LC-MS, we identified membrane proteins that may be associated with the activation of the virulence properties of the СD isolate ZvL2.

Chagas disease (CD) is a neglected tropical parasitic disease caused by the protozoan Trypanosoma cruzi. Unfortunately, the current etiological treatment for CD is unsatisfactory, due to the high toxicity and low cure efficacy of compounds, mainly during the chronic phase of this disease. Thus, the discovery of new drugs for the treatment of CD is urgent. In the present study, we report the synthesis of a series of guanidines and its evaluation in in vitro assays to determine the trypanocidal effects on the Tulahuen T. cruzi strain, transfected with a β-galactosidase reporter gene, in comparison to the cytotoxic effects on vertebrate cells. The most potent and selective compounds LQOF-G1 and LQOF-G29 were considered good drug prototypes and candidates for in vivo tests using mice. Both compounds possess an electron withdrawing group on the aniline moiety, namely a NO2 and Br group, respectively, which effectively decrease the electron density. LQOF-G29 stands out among the investigated compounds due to the replacement of the benzyl group by methyladamantane.

The electrical percolation of alternating current through two-phase polyethylene/graphite composite electrodes with different contents of graphite microparticles immersed in aqueous KCl solutions has been studied. Above the graphite content of the first percolation threshold, the electrochemical impedance response of this electrode is associated with an equivalent circuit of resistance Ru in series with a constant phase element CPE. An insulator material+conductive filler model is proposed in which the electroactive surface is considered as the intersection of the percolation cluster through the solid and the cluster associated with the interfacial region. CPE is analyzed assuming a distribution of micro-capacitors of the graphite particles in contact with the dielectric solution and inside the dielectric polymeric phase.

The dimethylaminophenyl-substituted silver phthalocyanine [dmaphPcAg] can be used as a UV-vis photoinitiator for in situ preparation of a silver/polymer nanocomposite. To verify early steps of the supposed mechanism of radical polymerization, we performed quantum chemical calculations of m[dmaphPcAg]q complexes with charges q = +1 to -2 in the two lowest spin states m, of a free ligand and its dehydrogenated/deprotonated products m[dmaphPcHn]q, n = 2 to 0, q= 0, -1 or -2, in the lowest spin states m. The calculated electronic structures and electron transitions of all the optimized structures in CHCl3 solutions are compared with experimental EPR and UV-vis spectra, respectively. The unstable 3[dmaphPcAg]+ species deduced only from previous EPR spin trap experiments was identified. In addition to 2[dmaphPcAg]0, our results suggest the coexistence of both reaction intermediates 1[dmaphPcAg]- and 3[dmaphPcAg]- in reaction solutions. Silver nanoparticle formation is a weak point of the supposed reaction mechanism from the energetic, stereochemistry, and electronic structure points of view.

The release of the active substance from the matrix modified-release tablets based on Kollidon®SR and chitosan depends on its solubility in the dissolution medium and on the composition of the matrix-forming polymers. The study is based on new oral matrix tablets based on Kollidon®SR and chitosan, formulated to optimize the low oral bioavailability of chlorzoxazone, a non-steroidal anti-inflammatory drug, a class II Biopharmaceutical Classification System. Nine types of chlorzoxazone matrix tablets were obtained using the direct compression method, and their combination at 1:1, 1:2, 1:3 chlorzoxazone/ excipients, 20%-40% (w/w) Kollidon®SR, 3-7% (w/w) chitosan and the auxiliary substances were formulated in constant concentrations. Pharmaco-technical characterization included the analysis of flowability and compressibility properties (flow time, friction coefficient, angle of repose, Hausner ratio, Carr Index), and of pharmaco-chemical characteristics (mass and dose uniformity, thickness, diameter, mechanical strength, Friability, degree of softening, in vitro release profile) of the tablets. Based on the initial evaluation of the pharmaco-technical analysis, pharmaco-chemical characteristics, and in vitro release profile, only three matrix tablet formulations (F1b, F2b, and F3b) were further tested. They were evaluated through Fourier-transform infrared spectrometry, X-ray Diffraction, thermogravimetry, differential scanning calorimetry, and in vitro dissolution tests. The three formulations were comparatively studied regarding the release kinetics of active substances using in vitro release testing. The results were analyzed by fitting into four representative mathematical models for the modified release oral formulations. In vitro kinetic study reveals a complex mechanism of release occurring in the first (0 - 2 hours) and second (2.0 hours – 36 hours) steps of drug release. Two factors have been calculated to assess the release profile of chlorzoxazone: f1 - the similarity factor and f2 - the factor difference. The results have shown that both Kollidon®SR and chitosan may be used as matrix-forming agents when combined with chlorzoxazone. In vitro dissolution tests revealed the F2b sample, data suggesting a faster drug release. The three formulations showed optimum pharmaco-technical properties and in vitro kinetic study, and they had tremendous potential to be used in oral pharmaceutical products for the controlled delivery of chlorzoxazone.

Soil organic matter (SOM) is essential for nutrient cycling and soil carbon (C) accumu-lation, both of which are heavily influenced by the quality and quantity of plant litter. Since SOM dynamics in relation to plant diversity are poorly understood we investigated the effects of willow variety and mixture, and site on the soil C stocks, SOM chemical composition and ther-mal stability. Using pyrolysis-field ionization mass spectrometry we analysed the top 10 cm of soil from two 7-year-old experimental sites in Germany and Sweden, with monocultures and mixtures of two willow varieties (Salix spp.) belonging to different species. Overall, site had the strongest effect on SOM quality. Results showed significant variability across sites for willow identity and mixture effects on C accumulation and SOM chemistry. In the German site (Ros-tock), yearly soil C accumulation was higher (p < 0.05) for variety ‘Loden’ (1.0 Mg C ha-1 year-1) compared to ‘Tora’ (0.5 Mg C ha-1 year-1), whilst in the Swedish site (Uppsala), both varieties ex-hibited similar soil C accumulation rates of around 0.6 Mg C ha-1 year-1. Willow variety identity significantly affected SOM quality at both sites, while mixing had minor effects. Our findings emphasize the significance of site-specific context and variety or species identity in shaping soil C accumulation in willow plantations.

Planar catechin (PCat), a natural antioxidant with a fixed 3D catechin structure on a plane, exhibits radical-scavenging activity approximately five times stronger than the conventional catechin. We synthesized a compound, PCat–TrOH, by binding Trolox (TrOH), an α-tocopherol analog, to PCat to enhance its antioxidant effect against oxidative stress, such as lipid peroxidation. TrOH shows radical-scavenging activity about 6.5 times greater than PCat, and PCat–TrOH exhibited a similar level of radical-scavenging activity to TrOH. Additionally, PCat–TrOH demonstrated twice the radical-scavenging activity against reactive oxygen species compared to PCat or TrOH. This compound is also expected to exhibit an excellent antioxidant effect against lipid peroxidation caused by radical chain reactions, through interactions with vitamin C, similar to that in the case of α-tocopherol.

Human-Computer Interaction, including technology-aided instruction, is beginning to focus on virtual reality (VR) technology due to its ability to support immersive learning, teaching through simulation, and gamification of learning. These systems can deliver high-level multisensory learning experiences that are important in the teaching of many subjects, especially those involving abstract concepts or requiring spatial skills, such as organic chemistry. Haptic experiences with VR, however, remain a challenge. In addition, development have focused on general entertainment/gaming; VR systems in chemistry implement simulations of the chemistry laboratory and other advanced systems whereas those that support safe, game-like, immersive and multisensory learning of organic chemistry with haptics at pre-university education levels are scarce. We developed the VR Multisensory Classroom (VRMC) as an immersive learning environment within a VR head-mounted display, where learners employ hand movements to build hydrocarbon molecules and experience haptic feedback through gloves with built-in sensors and hand-tracking with the Leap Motion system. We report here the evaluation of the first prototype by learners from diverse backgrounds who reported on the ability of the VRMC to support high engagement, motivation, interest and organic chemistry learning as well as diverse learning styles. The VRMC is a novel VR classroom that supports immersive learning in molecular organic chemistry with haptics for multisensory learning.

The goal of this study is to synthesize, determine the structure, and examine the antimicrobial properties of novel metal complexes of 2,4-dithiouracil and its derivatives. These complexes were obtained by mixing aqueous solutions of the corresponding metal salts with the ligand dissolved in DMSO and aqueous NaOH, using a metal-to-ligand ratio of 1:4:2. The structures of the new compounds were analyzed by melting point determination, microwave plasma atomic emission spectrometry (MP-AES) for Cu and Au, inductively coupled plasma optical emission spectrometry (ICP-OES) for S, ATR, solution and solid-state NMR and Raman spectroscopy. The interpretation of the complex spectra was aided by data for 2,4-dithiouracil obtained from 1H-1H COSY, DEPT-135, HMBC, and HMQC spectra. Additionally, the antimicrobial activity of these complex-es and the free ligands was evaluated against Gram-positive and Gram-negative bacteria, as well as yeasts.

New furan, thiophene and triazole oximes were synthesized through several-step reaction paths to investigate their potential for development of central nervous systems (CNS)-active and cholinesterase-targeted therapeutics in organophosphorus compound (OP) poisonings. Acute OP poisoning is still a challenge in treating patients despite the development of a large number of oxime compounds that should have the capacity to reactivate acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). The activity of these two enzymes, crucial for neurotransmission, are blocked by the OP, which has the consequence of disturbing normal cholinergic nerve signal transduction in the peripheral and CNS, leading to cholinergic crisis. Oximes in use have one or two pyridinium rings and cross the brain–blood barrier poorly due to the quaternary nitrogen. Following our recent study on 2-thienostilbene oximes, in this paper we described the synthesis of 63 heterostilbene derivatives out of which 26 oximes were tested as inhibitors and reactivators of AChE and BChE inhibited by OP nerve agents – sarin and cyclosarin. While the majority of oximes were potent inhibitors of both enzymes in micromolar range, we identified several oximes as BChE or AChE selective inhibitors with a potential for drug development. Moreover, even oximes were poor reactivators of AChE, four heterocyclic derivatives reactivated the cyclosarin-inhibited BChE up to 70%, and cis,trans-5 [2-((Z)-2-(5-((E)-(hydroxyimino)methyl)thiophen-2-yl)vinyl)benzonitrile] had comparable reactivation efficacy to the standard oxime HI-6. In silico analysis and molecular docking studies connected the kinetic data to the structural features of these oximes, and confirmed their productive interactions with the active site of the cyclosarin-inhibited BChE. Based on inhibition and reactivation and their ADMET properties regarding lipophilicity, CNS activity, and hepatotoxicity, these compounds could be considered for further development of CNS-active reactivators in OP poisoning as well as cholinesterase-targeted therapeutics in neurodegenerative diseases like Alzheimer’s and Parkinson’s.

Evaluation of drug permeability using cell monolayers is an important in vitro assay in the process of drug development, to identify compounds with favourable pharmacokinetics that may proceed to in vivo studies. When allowed to differentiate on permeable filters for at least 21 days, monolayers of Caco-2 cells develop morphological and functional properties similar to those of the intestinal epithelium. Permeability through Caco-2 monolayers is thus particularly relevant to assess drug absorption after oral administration. The major drawback of this assay is its very low throughput, with the cell monolayers being used in a single permeability assay. We have previously proposed a protocol to allow the re-use of the Caco-2 monolayer on additional permeability assays during the stable period and shown that cell monolayer integrity is maintained. In this work we evaluate the effect of re-use on the permeability of several reference compounds that permeate through passive pathways and show that the cell monolayers can be re-used twice in additional permeability assays. Preliminary results were also obtained regarding active transport pathways, and a new methodology is proposed to quantify the contribution from passive and active transport. This is a major step towards the full validation of the re-use methodology proposed, which at least triplicates the throughput of this important in vitro assay.

Diarrhea remains one of the leading causes of mortality worldwide, especially among children. Recent epidemiological studies conducted in developing countries identified Shigella species as the most predominant pathogenic bacteria responsible for diarrhea. Antimicrobial therapy is necessary for Shigella infections; however, the rapid emergence of resistance against existing antimicrobials in Shigella spp. poses a serious global health problem. To identify alternative antimicrobial compounds with activity against Shigella species, the pathogens responsible for bacterial diarrhea. In this study, we have applied antibacterial phenotypic screening to identify potent anti-Shigella compounds across a broad chemical diversity, including selected acetaminophen derivatives containing benzothiazoles backbone, and their combination with certain antibiotics. In continuation to our effort in searching potent antimicrobial compounds, we have found this time around that two acetaminophen derivatives containing benzothiazoles backbone (4a and 4b) could inhibit the growth of Shigella flexneri with common MIC value of 12.5 µg/ml. These compounds were established through a time-kill kinetics’ study to be bactericidal. Meanwhile, the 2-aminobenzothiazoles (1a and 1b) used for the synthesis of compounds 4 (a & b) were found to be poorly active (MIC: 100 µg/ml) against this pathogen. Combination studies of 4a and 4b with the least susceptible antibiotics (ceftriaxone and cotrimoxazole) demonstrated synergistic anti-Shigella activity. The present study demonstrates that the azobenzothiazole dyes 4 (a & b) can be repurposed as potential anti-Shigella compounds, which can serve as scaffolds for the development of new agents against infectious diarrhea caused by Shigella and other enteric pathogens, especially in developing countries.

The dielectric constant (ε) reflects the ability of a material to align and orient electrical dipoles within its structure in response to an externally applied electric field; the greater the polarizability of molecules, the greater the value of dielectric constant. In this study a data set of 86 polymers was investigated to develop a structure-property quantitative relations (QSPR) model to predict the dielectric constant in polymers. An initial set of 1273 descriptors was used to select a best set of descriptors and to construct two machine learning models with Gradient Boosting Regressor (GB_A and GB_B). The best performing model (GB_A) with 8 descriptors, exhibited a performance of (R2train) = 0.938 and (R2test) = 0.802. The models were internally validated by 5 folds cross-validation, demonstrating robustness. Additionally, using the Accumulative Local Effect (ALE) technique, we analyzed the relationship between the 8 descriptors involved and the impact of these descriptors to dielectric constant of polymers.

Materials based on platinum metals with very good catalytic activity were tested in the reduction of p–nitrophenol (pNP) to p–aminophenol (pAP). The majority of presented catalytic materials are based on the adsorption of p–nitrophenol on the surface of the catalyst simultaneously with molecular hydrogen, coming from sodium borohydride in an aqueous medium, which reduces it. In the present paper, a catalytic material based on osmium dispersed in n–decanol or n–dodecanol is presented, which also works as an emulsion membrane, for the absorption of p–nitrophenol and molecular hydrogen at the n–alcohol aqueous solution interface. The hydrogenation of p–nitrophenol is carried out in a reaction and separation column in which the acid receiving phase emulsion is dispersed in the osmium nanodispersion, in n–alcohols. This emulsion circulates from the base of the column to its upper part in co-current or counter-current with the source phase consisting of p–nitrophenol and sodium borohydride. Experiments show that the circulation of counter-current phases is superior to that in co-current, and the emulsion based on n–decanol is more efficient than the one based on n–dodecanol. The increase in the pH difference between the source and receiving phases leads to the increase in the conversion of p–nitrophenol to p–aminophenol. The efficiency of separation of the reaction product in the receiving phase is lower than the conversion at the same operating time. The apparent catalytic rate constant (kapp) of the new catalytic material based on the emulsion membrane with nanodispersion of osmium nanoparticles (0.1×10−3 for n–dodecanol and 0.9×10−3 for n-decanol) is lower by an order of magnitude compared to those based on adsorption on catalysts from platinum metal group. The advantage of the tested membrane catalytic material is that it extracts p–aminophenol in the acid receiving phase. The paper proposes a mechanism of the studied reduction system.

Green and sustainable electrocatalytic conversion of nitrogen-containing compounds to ammonia are currently in high demand in order to replace the eco-unfriendly Haber-Bosch process. Model catalysts for the nitrate reduction reaction were obtained by electrodeposition of metal Co, Fe and bimetallic Fe/Co nanoparticles from aqueous solutions onto a graphite substrate. The samples were characterized by the following methods: SEM, XRD, XPS, UV-vis spectroscopy, cyclic (and linear) voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Besides, the determination of electrochemically active surface was also performed for all electrocatalysts. The best electrocatalyst was a sample containing Fe-nanoparticles on the layer of Co-nanoparticles, which showed the Faradaic efficiency 58.2% (E=-0.785 V vs. RHE) at the ammonia yield rate of 14.6 μmol h-1 cm-2. An opinion was expressed on elucidation of the mechanism of coordinated electrocatalytic action of a bimetallic electrocatalyst. This work can serve primarily as a starting point for future investigations on electrocatalytic conversion reactions to ammonia using model catalysts of the proposed type.

Medicinal plants produce various bioactive molecules with potential anticancer properties with favorable safety profiles. We investigated the comprehensive composition of Vernonia amygdalina leaf extract and its cytotoxic effects via apoptosis in HeLa cells. The metabolomics approach was conducted to gather the metabolite profile of the extract. Proteomics was performed to understand the comprehensive mechanistic pathways of action. The apoptosis was visualized by cellular staining and the apoptotic proteins were evaluated. V. amygdalina leaf extract exhibited dose-dependent cytotoxic effects on both HeLa and Vero cells after 24 h of exposure, however, a higher concentration was required for Vero cells cytotoxicity. The metabolomic profile indicated that majority of metabolites were alkaloids, phenolic compounds, and steroids. The cytotoxic pathways involved the response to stress and cell death which was similar to doxorubicin. The upstream regulatory proteins, PTEN and XBP1, were significantly altered supporting the regulation of apoptosis and cell death. The levels of apoptotic proteins, JNK, p53, and caspase-9 were significantly increased. These provided strong evidence that V. amygdalina leaf extract related to the induction of apoptosis and highlighted its potential for the development of chemotherapy.

A numerical mechanism connecting ice algal ecodynamics with the buildup of organic macromolecules is tested within modeled pan-Arctic brine channels. The simulations take place offline in a reduced representation of sea ice geochemistry. Physical driver quantities derive from the global sea ice code CICE, including snow cover, thickness and internal temperature. The framework is averaged over ten boreal biogeographic zones. Computed nutrient-light-salt limited algal growth supports grazing, mortality and carbon flow. Vertical transport is diffusive but responds to pore structure. Simulated bottom layer chlorophyll maxima are reasonable, though delayed by about a month relative to observations due to uncertainties in snow variability. Upper level biota arise intermittently during flooding events. Macromolecular concentrations are tracked as proxy proteins, polysaccharides, lipids and refractory humics. The fresh biopolymers undergo succession and removal by bacteria. Baseline organics enter solely through cell disruption, so that the internal carbon content is initially biased low. By including exudation, agreement with dissolved organic or individual biopolymer data is achieved given strong release coupled to light intensity. Detrital carbon then reaches hundreds of micromolar, sufficient to support structural changes to the ice matrix.

The prevalence of sexual harassment and abuse in school sport, specifically from coaches to their athletes remains a concerning and pervasive issue. In an attempt to better understand and prevent specific coach-behaviours associated with such sexual misconduct, researchers have developed the Sexual Violence Questionaire in Sport. While the reliability of this measurement tool has been tested in anglo-saxon cultural contexts, it is not known whether the questionnaire is applicable to other cultural contexts. A sample of 146 (52 female, 94 male) Bachelor students from a university in the Basque Country participated in this cross cross-sectional study. The questionnaire was administered twice over a two-week period to assess test-retest reliability. The internal consistency of the Sexual Violence Questionaire in Sport was high, with Cronbach's alpha values of 0.891 for perceptions and 0.813 for experiences across all participants. Gender-specific analysis showed similar reliability, with females having slightly lower alpha values for perceptions. Significant differences between test and retest were found (10 from perceptions 2 from experiences). However, Cohen’s Kappa analysis showed significant agreement across all items. In conclusion, the study highlights the questionnaire’s overall reliability and suggests its effectiveness as a tool for measuring sexual violence in sports within the Spanish context. Nonetheless, the findings of this study underscore the need for further research to enhance the instrument's stability and to better understand gender differences in perceptions and experiences of sexual violence in sports contexts.

The present work reports the effective method for removal of inorganic and organic pollutants using membranes based on different carbonaceous materials. The membranes were prepared based on cellulose acetate (18 wt. %), polyvinylpyrrolidone as a pore generating agent (2 wt. %) and activated carbon (1 wt.%). Activated carbons were developed from residues after extraction of mushroom Inonotus obliguus using microwave radiation. It has been shown that addition of activated carbon the physical (porosity, equilibrium water content and permeability) and chemical (content of the surface oxygen group) properties of the membranes. The addition of carbon material has a positive effect on the removal of copper ions from their aqueous solutions by the cellulose-carbon composites obtained. Moreover, the membranes were proved to be more effective in removal of copper ions than iron ones and phenol. The membranes were found to show higher effectiveness in copper removal from a solution of the initial concentration 800 mg/L. The most efficient in copper ions removal was the membrane containing urea-enriched activated carbon.

Polycyclic polyprenylated acylphloroglucinols (PPAPs) comprise a large group of compounds of mostly plant origin. The best-known compound is hyperforin from St. John's wort with its antidepressant, antitumor and antimicrobial properties. Chemical synthesis of PPAP variants allows the generation of compounds with improved activity and compatibility. Here we studied two synthetic PPAP-derivatives, PPAP 23 and PPAP 53, as to their antimicrobial activity. While PPAP 23 is insoluble in water, PPAP 53, the sodium salt, is water-soluble. In vitro, both compounds exhibited good and comparable activity against methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus faecium. Both compounds had no adverse effects on Galleria mellonella wax moth larvae, even at high concentrations. However, they were unable to protect the larvae from infection with S. aureus because components of the larval coelom neutralized the antimicrobial activity; a similar neutralizing effect was also seen with serum albumin. In a septic arthritis model triggered by S. aureus PPAP23 decreased the formation of abscesses and bacterial load in kidneys, and in a mouse skin abscess model topical treatment with PPAP 53 resulted in an approximately two-fold reduction in S. aureus counts. PPAP 23 and PPAP 53 also showed high growth inhibiting activity against anaerobic Gram-positive pathogenic gut bacteria such as Clostridium perfringens and Clostridium difficile. Based on these results, we envision potential application of PPAP 23 and PPAP 53 in the topical treatment of wound infections with Gram+ pathogens, and their oral use in intestinal infections with C. difficile.

Industrial hemp (Cannabis sativa L.) is an attractive candidate for sustainable pest management due to its abundance of bioactive compounds with potential pesticidal properties. Solvent choice has a significant impact on the extraction efficiency of bioactive compounds. Deep Eutectic Solvents (DESs) are gaining popularity in extraction because they are safe and environmentally friendly, making them viable alternatives to organic solvents (OSs). This research first compared the extraction efficiency of OSs on the extraction of phytochemicals from the infloresences of two hemp varieties, Citrus and Cherry Dwarf. Inflorescences were extracted using three OSs, ethanol, ethyl acetate, and hexane. The highest level of cannabidiol (CBD; 0.69%) was extracted from Cherry Dwarf using ethanol while the level of delta-9 tetrahydrocannabinol THC (0.19%) was essentially the same in both. Therefore, Cherry Dwarf was selected to compare the extraction efficiency of DESs to the OSs. The DESs were choline chloride/ethylene glycol, citric acid/ethylene glycol, menthol/lauric acid, choline chloride/urea and choline chloride/glycerol. In the targeted analysis, choline chloride/ethylene glycol extracted the highest amount of CBD (0.87%) followed by choline chloride/urea (0.78%). As some DESs outperformed ethanol, the popular solvent for extracting cannabinoids, DESs are viable candidates to replace organic solvents.

The growing threat of antibiotic pollution in water systems demands innovative and sustainable remediation strategies. Nanocellulose-based magnetic metal-organic frameworks (MOFs) represent a cutting-edge solution for the adsorption and removal of antibiotics, leveraging their high porosity, magnetic properties, and environmentally friendly nature. This paper provides an in-depth review of recent advancements in nanocellulose-based MOFs, focusing on their synthesis, adsorption mechanisms, and applications in environmental remediation between 2020 and 2024. By summarizing key studies, we highlight their performance in targeting widely used antibiotics such as tetracyclines and fluoroquinolones. The integration of nanocellulose with MOFs not only enhances adsorption capacity but also offers easy recovery, recyclability, and environmental compatibility. This review explores their adsorption mechanisms, practical applications, and future research directions, contributing to the advancement of scalable and sustainable water treatment technologies.

Polyethylene terephthalate (PET) is one of the most produced plastic materials in the world. The emer-gence of microplastics and nanoplastics (MPs/NPs) as a significant environmental contaminant has become a matter of increasing concern. While the toxicological effects of PET NPs have been widely re-searched, there is a lack of methodologies for studying their accumulation. The present study introduces a novel method to monitor the distribution of PET NPs in germinating wheat (Triticum aestivum L.) seeds. This involves the functionalization of superparamagnetic iron oxide nanoparticles (SPIONs) with PET NPs (PET-fSPION) coupled with magnetic resonance microimaging (µMRI) to provide insight into their distribution within the seed. The present study has demonstrated that PET-fSPION accumulates in specific regions of germinating wheat seeds, including the shoot apical meristem, the radicle, the cole-optile, the plumule, and the scutellum. Furthermore, the accumulation of PET-fSPION has been shown to exert a discernible effect on spin-spin relaxation, as observed via MRI and quantitative T2 relaxation time analysis. The accumulation of PET NPs in embryo regions was also confirmed by SEM. Diffu-sion-weighted magnetic resonance imaging (DW-MRI) and non-invasive chemical shift imaging analyses demonstrated that PET NPs resulted in restricted diffusion within the highlighted areas, as well as an impact on lipid content. Our study reveals that using µMRI with fSPION provides a non-invasive method to monitor the biodistribution of PET nanoparticles in wheat seeds. Additionally, it offers valuable in-sights into the microstructural interactions of PET.

Silica on Silicon is a major optical integration platform, while the emergent class of integrated Laser written circuits' platform offers additionally high customizability, and flexibility for rapid prototyping. However, the inherent waveguides' low core/cladding refractive index contrast characteristic compared to other photonic platforms in silicon or silicon nitride, sets serious limitations for on-chip efficient coupling with single photon emitters, like semiconductor nanowires with quantum dots limiting the applications in quantum computing. A new light coupling scheme proposed here overcomes this limitation providing means for light coupling >50%. The scheme is based on the incorporation of an optical microsphere between the nanowire and the waveguide, properly optimized and arranged in terms of: size, refractive index, distance of microsphere between nanowire and waveguide. Upon suitable design of the optical arrangement, the photonic nanojet emitted by the illuminated microsphere excites efficiently the guided eigenmodes of the input channel waveguide, thus launching light with high coupling efficiency. The method is tolerant in displacements, misalignments, and imperfections and is fabricationally feasible by current state of the art techniques. The proposed method enables the on-chip multiple single photon emitters' integration thus allowing the development of highly customizable and scalable quantum photonic integrated circuits for quantum computing.

Background/Objectives: High-intensity anaerobic physical training frequently results in muscle damage among boxers and kickboxers, which can impede performance and recovery. Vibrational therapy (VT) and passive rest (PR) have been employed as methods to enhance muscular recovery and performance. This study evaluates the effectiveness of these two recovery methods on upper limb muscle strength and lactate levels in plasma after high-intensity exertion. Methods: Eighteen elite boxers and kickboxers, aged 19-32 years, underwent tests employing VT and PR as recovery methods in a controlled, crossover study. Muscle performance was assessed via isokinetic dynamometry, and lactate levels were measured pre-exercise, post-exercise, and post-recovery. The study adhered to the Declaration of Helsinki guidelines and was approved by the relevant bioethics committee. Results: The results showed that VT led to a faster recruitment of muscle fibers and improved muscle endurance as indicated by decreased fatigue work indices compared to PR. However, no significant differences were observed in peak torque or lactate levels between the two recovery methods. The VT group exhibited quicker recovery times in torque generation and better performance in fatigue resistance. Conclusions: VT appears to provide superior muscular recovery compared to PR following intense anaerobic effort, particularly in terms of muscle strength endurance and activation speed. These findings support the potential of VT in sports recovery protocols, although similar lactate response suggests that metabolic recovery rates are not significantly affected.

(1) Background: In this work, a series of benzimidazole derivatives containing colchicine-like and cathechol-like moieties with methyl group substitution in the benzimidazole ring were evaluated for their in vitro antiproliferative, pro-apoptotic and antioxidative activity against highly invasive breast cancer cell line MDA-MB-231 and related impairment of tubulin dynamics; (2) Methods: MTT assay was used to evaluate the antiproliferative activity. In vitro tubulin polymerization assay as well as docking analysis was applied to prove the alterations in tubulin polymerization. Immunofluorescent and DAPI staining reveal the pro-apoptotic potential of benzimidazole derivatives and the effect on tubulin’s dynamics in living cells. The antioxidant activity was evaluated by scavenging of H2O2 and hypochlorite ion and ortho-phenanthroline tests; (3) Results: The compounds containing colchicine-like moiety displayed significant growth inhibitory effect against cancer cell line as was highlighted the role of methyl functional group on the tubulin aggregation and blockage of mitosis. All compounds showed an ability to scavenge H2O2, while the compounds with cathecol-like moiety were more effective against hypochlorite ion and chelation of iron; (4) Conclusions: The benzimidazole derivative containing colchicine-like moiety and methyl group substitution in benzimidazole ring is a potential antiproliferative and microtubule destabilizing agent.

Water quality control employs techniques mostly targeting individual analytes; group detection is also practiced, but the choice of group methods is limited, which supports interest in developing such methods. We have examined an interaction of hypochlorite with a chlorine-containing heptamethine carbocyanine dye in the presence of 30 organic and inorganic model analytes that were found to induce diverse color changes in the system. The main supposed mechanisms are retardation of the dye oxidation with hypochlorite (presumably by scavenging chlorine radicals) and substitution of chlorine atom in the dye by the most nucleophilic analytes (amines, amino acids, proteins, DNA, phenol). The grass-green substitution product is more contrastingly visible against the dark-purple hypochlorite oxidation product of the dye than against the original emerald-green dye. The indicator reaction is monitored photographically for 10–40 min and the images are processed using principal component analysis (PCA) or linear discriminant analysis (LDA), allowing for data convolution for the complex color transitions. Nitrogen compounds are discriminated from the others, and more reactive analytes (tryptophan, cysteine, bovine serum albumin, and DNA) are detected in the presence of less reactive ones in natural water. The system is promising for the development of group assays for dissolved organic matter and discrimination of water samples.

The aim of the study was to assess the impact of two lengths of Nordic walking (NW) training interventions combined with time restricted eating (TRE) on improving body composition parameters, lipid profile, and levels of selected adipokines in women with disrupted body mass. Overweight and obese women (n=55, age: 21-85) were recruited. Four groups were selected: 6 weeks (SG6, n=13) and 12 weeks intervention (SG12, n=13); and two control groups: CON6 (n=13); and CON12 (n=13). The training sessions took place 3 times a week (60 minutes each) and were conducted outdoor under the supervision of professional coach. The training intensity was determined individually. The extended NW program combined with TRE induced a significant weight reduction in SG12 by 1.96 kg (p=0.010) and fat tissue by 1.64 kg (p=0.05). The proposed interventions did not affect LBM, TBW [kg], VFA and lipid profile. The LDL/HDL ratio changed with small size effect. Leptin concentration differed between groups (p=0.006), but not over time. For resistin, the differentiating factor was time (p=0.019, with lower results observed after the intervention). The change in leptin concentration was negatively correlated with its baseline concentration. Extended to 12 weeks, this intervention allows for an improvement in body composition. Neither 6 nor 12 weeks of training and fasting affected the lipoprotein profile.

Background/Objectives: Nail technicians frequently have musculoskeletal pain, which impairs their job performance. A high-risk profession linked to back discomfort that causes morbidity is nail technician. QEC is a tool used for observing and assessing risks in a work environment. The goal of this research is to assess the ergonomic risks, pain, and their relationship with posture among manicurists. Methods: The 35 nail technicians filled the assessment form which consists of occupational information, pain, European Community Respiratory Health Survey, Nordic Musculoskeletal Questionnaire and QEC worker part. Physicians assessed nail technicians’ workspace and QEC outcomes. Results: It was stated that they worked an average of 61.92±11.09 hours per week, served an average of 11±5 customers per day, and their condition lasted 53.96±36.51 months. There is a strong significant correlation between discomforts, time spent in occupation (p=0,000) and working hours. Manicure, pedicure, unwanted hair removal, correction of eyebrow were considered for ergonomic risk evaluation. Each occupation accompanied repeated bad postures. Most of them were scored in very high risk categorization for back static positions (more than 29 point). Conclusions: This study may be useful for nail technicians seeking ergonomic improvements in the areas of engineering, administration, behavior, or personal.

p-Toluenesulfonic acid is commercially available, non-toxic, cheap organic compound with robust stability. p-Toluenesulfonic acid is solid, non-corrosive and a strong organic acid that can be handled easily. Due to this p-toluenesulfonic acid could be the better replacement of other conventional acids like nitric acid, sulfuric acid, perchloric acid and AlCl3 in organic transformations. Moreover, p-toluenesulfonic acid could be used synergistically with other mode of catalysis like transition metal catalysis and photocatalysis. In recent years, the use of this solid organic acid in organic and polymer synthesis has grown tremendously. In this review, we present an overview of p-toluenesulfonic acid promoted various organic reactions with particular emphasis to the more recently reported methods. In some cases, we also detailed the understanding of the reactions by providing the reaction mechanism. Despite these advances, there are still many opportunities for the development of new reactions using PTSA. Industry and academia have become more conscious to adopt sustainable chemical processes using safer reagents and solvents and the use of PTSA in this context is highly significant. This review will inspire researchers for further reaction development employing p-toluenesulfonic acid.

This study explores the complexities of sport manager selection, investigating the impact of affirmative action, recruitment strategies, organizational culture, diversity initiatives in board selection, and career advancement insights from coaches' perspectives. To conduct this investigation, a purposive sampling technique was employed, selecting 65 prominent sports managers and coaches from Romania. Participants, aged between 35 to 58 years old, boasted an average of 10 to 20 years of sports experience and were chosen based on specific criteria, including academic qualifications. Data collection occurred over an extended period, spanning from fall 2022 to spring 2024, through semi-structured interviews with sport managers and coaches. The findings unveiled persistent challenges in effectively implementing affirmative action measures, as sport managers grapple with balancing the promotion of deserving candidates while maintaining continuity in board culture. Achieving meaningful diversity necessitates nuanced approaches that consider both candidate quality and cultural compatibility. Moreover, the study sheds light on coaches' perspectives when considering executive council positions, highlighting various pathways to career advancement. Recruitment practices prioritized informal methods, emphasizing board cohesion. Despite the recognized importance of diversity, challenges persist in selecting candidates solely based on demographic representation. The study provides valuable insights into promoting diversity and inclusivity within sports organizations' executive councils. Future research directions may include exploring longitudinal trends and delving into the qualitative experiences of underrepresented groups, with the aim of advancing understanding and promoting equity within sports organizations.

Hydrogen is the lightest atom and composes roughly half of the atomic content in macromolecules, yet their location can only be inferred or predicted in most macromolecular structures. This is because hydrogen can rarely be directly observed by the most common structure determination techniques (such as X-ray crystallography and electron cryo-microscopy). However, knowledge of hydrogen atom positions, especially for enzymes, can reveal protonation states of titratable active site residues, hydrogen bonding patterns, and the orientation of water molecules. Though we know they are present, this vital layer of information, which can inform a myriad of biological processes, is frustratingly invisible to us. The good news is that, even at modest resolution, neutron crystallography (NC) can reveal this layer and has emerged this century as a powerful tool for elucidating enzyme catalytic mechanisms. Due to its strong and coherent scattering of neutrons, incorporation of deuterium into the protein crystal amplifies the power of NC. This is especially true when solvation and the specific participation of key water molecules are crucial for catalysis. Neutron data allow the modeling of all three atoms in water molecules and have even revealed previously unobserved and unique species such as hydronium (D3O+) and deuteroxide (OD-) ions as well as lone deuterons (D+). Herein, we briefly review why neutrons are ideal probes for identifying catalytically important water molecules and these unique water-like species, limitations in interpretation, and four vignettes of enzyme success stories from disparate research groups. One of these groups was that of Dr. Chris G. Dealwis, who died unexpectedly in 2022. As a memorial appreciation of his scientific career, we will also highlight his interest and contributions to the neutron crystallography field. As both the authors were mentored by Chris, we feel we have a unique perspective on his love of molecular structure and admiration for neutrons as a tool to query those structures.

Herein, we have reported the synthesis and characterization [single crystal X-ray diffraction technique, spectroscopic etc.] of two new Ni(II) and Zn(II) coordination compounds viz. [Ni(2,6-PDC)2]2[Ni(en)2(H2O)2]2[Ni(en)(H2O)4]·4H2O (1) and [Zn(2,6-PDC)(Hdmpz)2] (2) (where, 2,6-PDC = 2,6-pyridinedicarboxylate, en = ethylene-1,2-diamine, Hdmpz = 3,5-dimethyl pyrazole). Compound 1 is found to crystallize as a multicomponent Ni(II) compound with five discrete complex moieties; whereas, compound 2 is a mononuclear compound of Zn(II). Deep analysis of the crystal structure of compound 1 unfolds unusual dual enclathration of guest complex cationic moieties within the supramolecular host cavity stabilized by anion‒π, π-stacking, N‒H⋯O, C‒H⋯O and O‒H⋯O hydrogen bonding interactions. Interestingly, further enclathration of a complex cationic moiety is observed within another supramolecular host cavity formed involving anionic complex moieties and lattice water molecules in 1. Again, the crystal structure of compound 2 is stabilized by the presence of unconventional C‒H⋯π(chelate ring) interactions along with C‒H⋯O, C‒H⋯N hydrogen bonding, π-stacking, C‒H⋯π(pyridyl) interactions. These non-covalent interactions have been further studied theoretically using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) computational tools. The computational study displays that π-stacking or H-bonds greatly tune the directionality of compound 1 although non-directional electrostatic forces dominate energetically. For compound 2, combined QTAIM/NCI plot analysis confirms the presence of unconventional C‒H⋯π(chelate ring) interaction along with other weak interactions obtained from the crystal structure analysis. Further, the individual energy contributions of these weak yet significant non-covalent interactions have also been determined computationally.

Seeds from several Ribes taxa were surveyed for phenolic compounds and in vitro antiproliferative activity against HT-29 colorectal cancer cells. Total phenolic compounds were analysed through the Folin-Ciocalteu procedure, while phenolic profiles were analysed by LC coupled to a single mass spectrometer Orbitrap using an electrospray interface (ESI). Antitumor effects were established using the MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay. Total phenolics ranged from 11.4 in R. alpinum to 94.8 mg of caffeic acid equivalents (CAE)/g in R. nigrum 'Koksa'. Concerning phenolic compounds, four were hydroxylated benzoic acids, four cinnamic acid derivatives, eight flavonoids, and nine flavonoid glycosides. The growth inhibition against HT-29 cancer cells was exercised much better by R. nigrum 'Koksa' and Ribes 'Erkeeni' (GI50 37 and 42 µg/ml). All Ribes extracts, except R. nigrum 'Hara katarlik', showed higher activity than that of R. rubrum (GI50 at 72 h: 99 µg/ml). Interestingly, the highly bioactive extract from Ribes 'Erkeeni' contains all detected phenolics, while R. nigrum 'Koksa' lacks only populnin. Therefore, the high bioactivity found for such extracts could be due to a synergy due to all detected compounds. This work constitutes a comprehensive action for expanding knowledge on the phenolic profiles and antitumor activity of GLA-rich Ribes seeds.

Theoretical studies on the generation of nondiffracting and nondispersive light pulses and their experimental implementation are one of the renowned problems within electromagnetics. Current technologies enable creation of short-duration pulses of a few cycles with high power and fluency. An application of these techniques to the field of nondiffracting and nondispersive pulses requires a proper mathematical description of highly focused vector pulses. In this work, we study vector optical bullets in a dielectric medium with different polarization structures: linear, azimuthal, and radial. We report the differences caused by the vector model compared to the scalar model. We analyze effects caused by superluminal, subluminal, or even negative group velocity on properties of vector optical bullets inside a dielectric material.

Evidence suggests that COVID-19 infection can cause lasting health consequences. Multidiscipli-nary rehabilitation services have been recommended to reduce the sequalae. However, the effec-tiveness of physical exercise interventions remains insufficiently documented. The aim of this study was to develop and implement a specific and well tolerated protocol-based, intervention to reduce muscle weakness in older adults impacted by COVID-19. Forty six older adults random-ized into Intervention and Control Groups. Isometric and isokinetic strength assessments were conducted for selected muscle groups using JBA Staniak® torquemeter and Biodex System 3 dy-namometer. Functional abilities were evaluated with the Time Up and Go test and Chair Stand Tests. Men in intervention group demonstrated a significant improvement in static conditions for knee flexors (KF), trunk extensors (TE) and trunk flexors (TF) and in dynamic conditions for knee extensors (KE). Women in intervention group showed significant improvement in static condition for EF, KF, TE and TF and in dynamic for a KE and for a KF. The interaction GROUP x TESTING SESSION was significant for Chair test (s) and Chair test (n). Our results demonstrate the effec-tiveness of a well-tolerated, protocol-based approach that can be used to diminish long lasting functional deficits in post-covid survivors.

Magnetic Fe3O4 nanoparticles (MNPs) are becoming more important every day in drug targeting. We prepared here MNPs in a simple one-step reaction by following the solvothermal method assisted by azide and alkyne functionalized polyethylene glycol (PEG400) polymers, as well as by PEG6000 and the polyol -cyclodextrin (CD). The composition, morphology, and structure of the nanospheres were characterized using Transmission Electron Microscopy (TEM), Nuclear Magnetic Resonance (NMR), X-Ray Diffraction Diffractometry (XRD), Atomic Force Microscopy (AFM), Fourier-Transform Infrared Spectroscopy (FT-IR), Matrix-Assisted Laser Desorption/Ionization (MALDI) and Vibrating Sample Magnetometry (VSM). The obtained nanoparticles (@Fe3O4-PEGs and @Fe3O4-CD) showed diameters between 90-250 nm, depending on the polymer used and the Fe3O4·6H2O precursor concentration, typically, 0.13 M, 200 °C, and 24 h of reaction. MNPs exhibited superparamagnetic properties with high saturation of magnetization at room temperature, reaching values of 59.9 emu/g (@Fe3O4-PEG6000), and no ferromagnetism. Likewise, they showed temperature elevation after applying an alternating magnetic field (AMF) in all cases, obtaining Specific Absorption Rate (SAR) values of up to 51.87 ± 2.23 W/g in the case of @Fe3O4-PEG6000. Both PEGs and the βCD played a crucial role as electrostatic stabilizers in the formation of Fe3O4 nanospheres, providing a polymeric/polyol coating around the magnetic cores. Additionally, the formed systems are susceptible for click chemistry, as was demonstrated in the case of the cannabidiol-propargyl derivative (CBD-Pro), which was synthesized and covalently attached to the azide functionalized surface of the system @Fe3O4-PEG400-N3. Prepared MNPs are highly dispersible in water, remaining in suspension for over 3 days, and non-toxic in the T84 human colon cancer cell line, indicating that they are ideal candidates for biomedical applications.

Modern organic synthesis is majorly focused on developing environmentally benign synthetic protocols by employing green chemistry principles. Accordingly, in our recent research work, we herein report the use of modified supramolecular host cyclodextrin as an effective solid based green catalyst for accessing structurally diverse and medicinally relevant pyrimidone architectures. The catalyst and the synthesized compounds 4 (a-r) were characterized using FT-IR, NMR and GC-Mass spectroscopy. Major highlights of the reported work include: atom economical process, extremely milder reaction conditions, operational simplicity, high isolated yields, and excellent catalyst turnover number. The molecular docking studies suggest that the compound 4n has the hydrogen bonding, hydrophobic and π-pair interactions with the active site of active sites of CXT M 15 receptor.

In this follow-up study, we aimed to assess the effectiveness of the “I do not smoke, I exercise”, anti-smoking preventive health education program. The program was based on the Theory of Planned Behavior supplemented with life-skills teaching and targeted at high school students. The intervention comprised ten one-hour online sessions, administered by physical education instructors. The study cohort comprised 222 students (109 boys, 113 girls) from 11 secondary schools, with an average age of 16.42 ± 1.36 years. Data collection involved pre- and post-intervention self-assessment questionnaires. The examined variables included attitudes towards smoking, intention to smoke, subjective norm, perceived behavioral control (PBC), knowledge about smoking, smoking behavior, exercise behavior, attitudes toward the program's implementation, and satisfaction with the program. Separate paired samples t-test revealed a significant improvement in students' knowledge about smoking, perceived behavioral control, and overall program satisfaction following the intervention. However, no significant changes were observed in the remaining variables. These findings suggest that the health education smoking prevention intervention incorporates techniques and strategies that influence the Perceived Behavioral Control variable, emphasizing students' strong interest in educationally theorized programs integrating technology into their design. Future studies should consider further examination of tobacco control strategies within the high school context.

Fibroin-chitosan composites, especially those containing nanohydroxyapatite, show potential for bone tissue regeneration. The physicochemical properties of these biocomposites depend on the compatibility between their components. In this study, the intermolecular interactions of fibroin and chitosan were analyzed using a molecular dynamics approach. Two types of systems were investigated: one containing acetic acid and the other containing calcium (Ca²⁺) and hydrogen phosphate (HPO₄²⁻) ions mimicking hydroxyapatite conditions. After obtaining the optimal equilibrium structures, the distributions of several types of interactions including hydrogen bonds, ionic contacts, and hydrophobic contacts along with the structural and energetical features were examined. The calculated binding energy values for the fibroin-chitosan complexes confirm their remarkable stability. The high affinity of fibroin for chitosan can be explained by the formation of a dense network of interactions between considered biopolymers. These interactions were found to be primarily hydrogen bonds and ionic contacts involving ALA, ARG, ASN, ASP, GLN, GLU, GLY, LEU, PRO, SER, THR, TYR, and VAL residues. As it was established, the complexation of fibroin with chitosan maintains the β-sheet conformation of the peptide. β-Sheet fragments in fibroin are involved in the formation of significant amount of hydrogen bonds and ionic contacts with chitosan.

In the text, the synthesis and characteristics of the novel ONS-type vanadium(V) complexes with thioanilide derivatives of amino acids are described. They have shown inhibition of human protein tyrosine phosphatases (PTP1B, LAR, SHP1 and SHP2) in the submicromolar range, as well as inhibition of non-tyrosine phosphatases (CDC25A and PPA2) similar to bis(maltolato)oxovanadium(IV)(BMOV). The ONS complexes increased [14C]-deoxy-D-glucose transport into C2C12 myocytes, and one of them, VC070, also enhanced this transport in 3T3-L1 adipocytes. These complexes inhibited gluconeogenesis in hepatocytes HepG2, but none of them decreased lipid accumulation in the non-alcoholic fatty liver disease model using the same cells. Compared to the tested ONO-type vanadium complexes with 5-bromosalicylaldehyde and substituted benzhydrazides as Schiff base ligand components, the ONS complexes revealed stronger inhibition of protein tyrosine phosphatases, but the ONO complexes showed greater activity in the cell models in general. Moreover, the majority of the active complexes from both groups showed better effects than VOSO4 and BMOV. Complexes from both groups activated AKT and ERK signaling pathways in hepatocytes to a comparable extent. One of the ONO complexes, VC068, showed activity in all of the above models, also including glucose utilization in the myocytes and glucose transport in insulin-resistant hepatocytes. The discussion section explicates the results within the wider scope of the knowledge about vanadium complexes.

In this article, we describe a simple procedure for evaluating the sterility of nutrient media using a shear-horizontal surface acoustic wave (SH-SAW) biosensor. We used the SH-SAW biosensor platform to monitor the time-dependent phase responses of the material for the media that binds to a monolayer of 3-mercaptopropanyl-N-hydroxy succinimide on the biosensor surface. Increases in the phase shift less than 50% of the starting phase shift recorded 180 minutes after the sterilization indicate a successful sterility test of the media. Our devices were then applied to sterility testing using a viable Escherichia coli (E. coli) K-12 solution to confirm our hypothesis. Filtered LB Broth was the negative control, and a 24-hour culture of E. coli was the positive control. Before testing, the cell solution was pelleted, the media decanted and then replaced with a 1x phosphate-buffered saline solution (1x PBS). Since we know that the N-hydroxysuccinimide residues will bind to amine groups, only in cases where microbial species are present will the surface binding increase greater than 50%. We confirmed our hypothesis using SH-SAW biosensors and overnight E. coli cultures. The sensitivity for our 250 MHz quartz SH-SAW sensors was calculated based on the response from the E. coli K-12 solution over the linear dynamic range, which appears to be 2x104 – 2x107 CFU per ml and has a sensitivity of S = 1.655x105 o m2 Kg-1. The limit of detection (LOD) for these sensors was calculated to be approximately 2x10-9 grams (g) which is estimated to be approximately 2,000 Escherichia coli (E. coli) K-12 cells. However, the sensitivity and insertion loss remained approximately unchanged before and after coating the sensor with 3,3'-Dithiobis(succinimidyl) Propionate (DSP).

Previous studies showed that some lamellarin-resembling annelated azaheterocyclic carbaldehydes and related imino adducts, sharing the 1-phenyl-5,6-dihydropyrrolo[2,1-a]isoquinoline (1-Ph-DHPIQ) scaffold, are cytotoxic in tumor cells and may reverse multidrug resistance (MDR) mediated by P-glycoprotein (P-gp). Herein, we synthesized and evaluated for their antiproliferative activity in four tumor cell lines (RD, HCT116, HeLa, A549) and ability of inhibiting P-gp-mediated MDR some ten diversely substituted 1-Ph-DHPIQ derivatives bearing at position 2 carboxylate groups (COOH, COOEt), nitriles (CN) and Mannich bases (e.g., morpholinomethyl derivatives). Lipophilicity parametrization and molecular docking calculations improved the understanding of the structure-activity relationships in cytotoxicity and P-gp inhibition of the investigated 1-Ph-DHPIQs, which led us to disclose a novel Mannich base HCl salt (8b’), which proved to be cytotoxic to all the tested tumor cell lines in the low micromolar range (IC50 &lt; 20 M) and to inhibit in-vitro the efflux pumps P-gp and MRP1 responsible for MDR, with IC50s of 0.45 and 12.1 M, respectively.

Circadian rhythm (CR) influences various physiological functions, including physical and cognitive performance, which fluctuate throughout the day. The present study aimed to investigate the combined and separate effects of CR and physical fatigue on cognitive and physical performance. A sample of 18 amateur athletes was subjected to a series of tests at three different times of the day: morning, afternoon, and evening. Fatigue was induced following isokinetic concentric exercise combined with a 20-minute treadmill run, followed by assessments of selected physical and cognitive tasks. Repeated measures ANOVA did not reveal an interaction between CR and fatigue in cognitive performance (p &gt; 0.05). However, a significant main effect of fatigue was observed in visual reaction time (VisRT) across all three time points. Moreover, peak torque (PT) and peak torque fatigue index (PTFI) showed significant differences between the three times of the day, peaking in the evening. Although we found no interaction between CR and physical fatigue state on selected cognitive parameters at the three times of day, a separate effect of fatigue on cognitive performance was identified. Additionally, physical parameters exhibited peak values occurring in the evening hours. Future research should further explore underlying mechanisms that potentially influence cognitive performance at different times of the day.

This study aimed to evaluate the effects of Blazepod technology when incorporated with various training regimens on the essential elements of physical fitness in volleyball, such as agility, speed, visual response time, and vertical leap. Thirty-six participants (age :17.33±0.48 y, height: 183.78±6.34 cm, weight: 77.14±5.16 kg) were in-volved in this study. In randomized design, three equal groups with two experimental groups and one control group were involved in the study over a period of six weeks: (GE1) used Blazepod technology to workout at a low level; (GE2) used Blazepod technology to workout at a higher intensity; (CG) did not employ Blazepod technology, but it adhered to the same fundamental training curriculum. We conducted agility, speed, reaction time, and vertical jump tests before, midway and after the study to determine optimal training volume, intensity, and frequency. A significant main effect of time (P0.01), and time×group interaction (P>0.001) were found for all tests. Post hoc test showed that the two experimental groups gadget significantly improved in all performance variables (P

In this review, we have included current information on the use of photodynamic therapy in the treatment of gliomas. We mainly focused on the discussion and regarding the use of photodynamic therapy in patients with genetically determined syndromes that are associated with an increased risk of glioma. The review also uses information on genetic syndromes that are associated with an increased risk of glioma.

Cancers, a large and heterogeneous group of malignancies, are becoming an increasingly important cause of premature mortality worldwide. 2% of these are primary CNS tumors, of which 24% are gliomas. These tumors are diverse, but what they have in common is one of the most unfavorable prognoses among all cancers. A patient's future varies depending on the grade of the diagnosed glioma. To date, however, no standard treatment for grade IV has been established. All glioblastomas eventually undergo progression or recurrence. The current standard of treatment, which includes surgical intervention, radiation therapy and chemotherapy, is therefore far from sufficient. Work is constantly underway to discover a new, effective form of glioma therapy. Photodynamic therapy (PDT) may be one of them. It involves the local or systemic application of a photosensitive compound - a photosensitizer (PS), which accumulates in the affected tissues. Photosensitizer molecules absorb light of the appropriate wavelength, initiating activation processes leading to the formation of reactive oxygen species and selective destruction of inappropriate cells. Currently, this method has been approved for the treatment of several cancers. Research focusing on the effective use of PDT in glioma therapy is already underway, with promising results. In our work, we present molecular insights into PDT of glioma. Based on the available literature, we analyze and systematize the impact of various molecules, proteins, transporters and transmitters on the efficacy of PDT and the effect of PDT on their expression. In addition, we highlight gaps in current knowledge and point out directions for future research that may contribute to the efficacy of PDT glioma.

Lean body mass (LBM) is correlated with powerlifting performance in athletes competing in different bodyweight classes. However, it remains unknown whether changes in LBM are correlated with performance changes in powerlifters preparing for a competition. Aim of the study was to investigate the changes in LBM and performance in powerlifters preparing for a competition. Eight male powerlifters (age 31.7±9.8years, height 1.77±0.06m, weight 99.2±14.6kg) and three female powerlifters (age 32.7±16.3years, height 1.54±0.06m, weight 66.6±20.9kg), participated in the study. Athletes followed individualized periodized training programs for 12 weeks aiming to maximize their performance for the national championship. Maximum strength (1-RM) in squat, bench press, and deadlift, body composition, grip strength, anaerobic power, quadriceps’ cross sectional area and vastus lateralis muscle architecture were measured before and after the training period. Significant increases were found after the training period in squat (5.8±7.0%, P

Yoga promotes acceptance, compassion, physicality, active postures, mental and emotional awareness, and spiritual benefits. It involves breath techniques, postures, and body locks, maintaining balance and strength. It's based on ethical principles. Beyond simple performance, swimming is a catalyst for overall well-being. Complementarily, yoga serves as an invaluable adjunct for swimmers, enhancing flexibility, strength, and body awareness - a triad essential to aquatic excellence. The confluence of yoga and swimming, particularly through the practice of aqua yoga asanas, presents a new paradigm for both athletes and non-performers alike. Athletes who embrace the harmonious fusion of swimming and yoga unearth the potential for achieving not just athletic mastery but also a more balanced and fulfilling lifestyle. This blend provides a route not only to enhance performance in the water but also to elevate the overall quality of life. We examined the feasibility of incorporating yoga and swimming practice into Romanian subjects' lifestyles, designing a factor analysis in SmartPLS software, based on an online survey. The study assesses the participants' knowledge of yoga's theory and philosophy, as well as their perceptions of the swimming practice's benefits for social and health issues. According to our study, Romanian participants practice yoga and swimming as often as possible to reduce stress, improve concentration for work-related tasks, and improve joint elasticity, balance, and muscular tone. Thus, Yoga and swimming are substitutes for other approaches in prevention and therapy.

We present an open-source Star Tracker (ST) for Attitude Determination. Our implementation makes use of open source software of common usage in astronomy running on a Raspberry Pi 2 platform. The developed platform is open and available for parties interested in further development. Evaluation of the system showed that the ST is suitable for Cubesats of 2U or larger. The ST platform is capable of solving the Lost-In-Space (LIS) problem. Currently, the average accuracy reached of the algorithm is close to 5 seconds of arc with an average processing time of 75 seconds. However, a average accuracy of about 3 minutes of arc can be reached with 35 seconds in average processing time. We also describe the evaluation procedure, the found conclusions of this procedure, in particular the section of the algorithm where most of the processing time is spent and other possible source of errors not included in this study.

The Julia-Kocienski olefination reaction has become over past 30 years since its discovery one of the key C-C connective methods that is used in the late-stage natural product synthesis. The reaction proceeds under mild reaction conditions, with wide substrate scope and functional group tolerance, and with high (E) selectivity. In this review, we discuss the reaction from a mechanistic point of view and disclose key features that play an important role in reaction selectivity. Finally, the mechanistic aspects of the newly developed modification of the Julia-Kocienski reaction, which allows the formation of both (E) and (Z) olefins, from the same reaction partners, are discussed.

This paper presents the results of investigations on the kinetic of Brilliant Blue FCF (BB) discoloration reactions in aqueous solutions with different ozone concentrations and pH conditions. Kinetic studies involve knowledge of the structure and properties of the dye and ozone, as well as the experimental conditions. In general, scientists admit that the predominant oxidation pathway is direct (by free oxygen atoms) or indirect (by free hydroxyl radicals), it will depend on influencing factors such as: the physicochemical properties of the dye, the pH of the aqueous solution, ozone concentration, reaction time and the contact mode with/without stirring. In the experimental research, two pathways were chosen following CBB = f(t): 1. constant dye concentration and different ozone concentration on the concentration range (100 - 250 mg/L) at three pH media (acidic, neutral and basic) with and without stirring; 2. Constant concentration of ozone and different dye in the range of concentrations (2.5 - 10 mg/L) under the conditions of point 1. With obtained experimental data the curves CBB = f(t) were drawn and were processed by the integral method of classical kinetic based on first and second order equations. Unfortunately, this simple procedure this not yield any minim full results and any pH level. The rate constants been negative and/or the reaction order been dependent on initial conditions. Due to its structure, the BB dye has several chromophore groups, thus multiple attack centers, resulting in more oxidation by-products, which is why the 1H - NMR spectrum of BB discoloration with ozone was recorded.

Background: Scientific literature on COVID-19 is still limited about long-term impacts on the all-body systems and they treatments. The aim of the study was to create a safe protocol-based in-tervention to improve functional and equilibrium abilities in older adults impacted by COVID-19. Methods: The study completed 46 people (intervention group: n=26; control group: n=20). Re-sistance training (RT) was held twice a week, 60 min per session for 8 weeks. The postural stability and quality of life questionnaire (WHQOOL) were conducted during pre- and post-testing. Results: Results indicated significant differences in overall stability index (OSI) with eyes open (EO), ante-rior-posterior stability index (APSI) EO, fall risk index 6-2 (FRI6-2) values in males (p

Despite the recognized influence of body mass on combat techniques, the relationship between body segment mass (BSM) and combat moves remains unexplored. This study aimed to examine the relationship between striking arm mass (SAM), kicking leg mass (KLM), and body mass (BM) with the dynamic forces of the direct punches (DP), palm strikes (PS), elbow strikes (ES), front kicks (FK), and countermovement jumps (CMJ) performance. Sixteen male military cadets (22.3 ± 1.8 years, 181.4 ± 7.0 cm, 82.1 ± 8.5 kg) performed combat techniques, with performance measured by using a force plate and body segment mass assessed by Dual-energy X-ray absorptiometry. Spearman's correlation analysis, the Wilcoxon test, and Cohen's d were applied. Results indicated the relationship between KLM or BM and FK impulse (r = 0.64, p = 0.01; r = 0.52, p = 0.04, respectively) and CMJ impact force (r = 0.80, p ≤ 0.01; r = 0.70, p ≤ 0.01, respectively). Moreover, FK peak and impact forces were moderately correlated with CMJ jump height (r = 0.74, p ≤ 0.01; r = 0.77, p ≤ 0.01). The highest relationship was found between KLM and FK impulse; however, the difference in variability explained by KLM versus body mass is only 12%. This suggests that knowledge of BSM did not provide a significantly better estimate of the dynamic forces of the punches and FK than BM.

The aim was to identify if surface electromyography (sEMG) parameters are indicative of post-activation potentiation (PAP)/post-activation performance enhancement (PAPE), in terms of twitch potentiation and voluntary performance. Three databases were used in March 2024, with the following inclusion criteria: (a) original research, assessed in healthy human adults, (b) sEMG parameters were measured. The exclusion criteria were: (a) studies with no PAP/PAPE-protocol, (b) non-randomized control trials. The following data were extracted: study characteristics/demographics, PAP/PAPE-protocols, sEMG parameters, twitch/performance outcomes, and study findings. A modified physiotherapy evidence database (PEDro) scale was used for quality assessment. Fifteen randomized controlled trials (RCTs), with a total of 199 subjects were included. The M-wave amplitude (combined with a twitch torque outcome) was shown to generally be indicative of PAP. The sEMG amplitude (in some muscles) were found to be indicative of PAPE during ballistic movements, while a small decrease in the MdF (in certain muscles) were shown to reflect PAPE. Changes in the Hmax/Mmax ratio were found to contribute (temporally) to PAP, while the H-reflex amplitude was shown to be neither indicative of PAP nor PAPE. This review provides preliminarily findings suggesting that certain sEMG parameters could be indicative of PAP/PAPE. However, future research is warranted.

The accuracy of cosmic ray observation by the Large High Altitude Air Shower Observatory Wide Field-of-view Cherenkov/fluorescence Telescope Array (LHAASO-WFCTA) is influenced by variations in aerosols in the atmosphere. The solar photometer (CE318-T) is extensively utilized within the Aerosol Robotic Network as a highly precise and reliable instrument for aerosol measurements. With this CE318-T 23, 254 sets of valid data samples in 394 days from October 2020 to October 2022 at the LHAASO site were obtained. Data analysis revealed that the baseline Aerosol Optical Depth (AOD) and A˚ngstro¨m Exponent (AE) at 440-870 nm (AE440−870nm) of the aerosols were calculated to be 0.03 and 1.07, respectively, suggesting that the LHAASO site is among the most pristine regions on Earth. The seasonality of the mean AOD are the order of spring &gt; summer &gt; autumn = winter. The monthly average maximum of AOD440nm occurred in April (0.11 ± 0.05) and the minimum was in December (0.03 ± 0.01). The monthly average of AE440−870nm exhibited slight variations. The seasonal characterization of aerosol types indicated that clean continental background aerosol predominated in autumn and winter, which is the optimal period for the absolute calibration of the WFCTA. Additionally, the diurnal daytime variations of AOD and AE across the four seasons are presented. Our analysis also indicates that the potential origins of aerosol over the LHAASO in four seasons were different and the atmospheric aerosols with higher AOD probably originate mainly from Northern Myanmar and Northeast India region. These results provide a baseline for comparison to the future on-site measurement of extinction coefficient profile and aerosol phase function by LHAASO-WFCTA, also enrich the valuable materials on aerosol observation in the Hengduan Mountains and Tibetan Plateau.

Two new Mn(II) and Zn(II) metal-organic compounds of 1,10-phenanthroline and methyl benzoates viz. [Mn(phen)2Cl2]2-ClBzH (1) and [Zn(4-MeBz)2(2-AmPy)2] (2) (where, 4-MeBz = 4-methylbenzoate, 2-AmPy = 2-aminopyridine, phen = 1,10-phenanthroline, 2-ClBzH = 2-chlorobenzoic acid) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction techniques. Crystal structure analysis of the compounds reveals the presence of various non-covalent interactions which provides stability to the crystal structures. Crystal structure analysis of the compound 1 reveals the formation of supramolecular dimer of 2-ClBzH enclathrated within the hexameric host cavity formed by the neighboring monomeric units. Compound 2 is a mononuclear compound of Zn(II) where flexible binding topologies of 4-CH3Bz is observed with the metal centre. Moreover various non-covalent interactions such as lp(O)-π, lp(Cl)-π, C‒H∙∙∙Cl, π-stacking interactions as well as N‒H∙∙∙O, C‒H∙∙∙O and C‒H∙∙∙π hydrogen bonding interactions are found to be involved in plateauing the molecular self-association of the compounds. The remarkable enclathration of the H-bonded 2-ClBzH dimer into a supramolecular cavity formed by two [Mn(phen)2Cl2] complexes has been further studied theoretically using density functional theory (DFT) calculations, non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) computational tools. Synergistic effects have been also analysed using molecular electrostatic potential (MEP) surface analysis.

While the number of publications on wine and health is steadily increasing, ranging from molecular level to epidemiological studies, often with contradictory results, little attention has been given to an holistic approach. In this review some unusual concepts are considered, such as phytocomplex, vehicle and the Matrix effect. As an example, three mono/polyphenols present in wine, Tyrosol, Hydroxytyrosol and Resveratrol, have been selected and the consequences of respecting, disregarding or ignoring the Matrix effect are shown. Underestimation of the wine Matrix effect could lead to deceiving results, as in the case of de-alcoholized wine or wine-compound-based nutritional supplements,or in emphasizing a single component toxic activity, in this case alcohol, ignoring the specific protective action at molecular level of other compounds (polyphenols) present in the same Matrix. The dark side of Matrix effect is also discussed. It is suggested that specificity of wine should be always taken in consideration by public health Authorities.

Asparagus shoots are worldwide consumed, although most of such species have a restricted range, and several taxa still remain unstudied. In this work, a total of four taxa from different locations were scrutinized and compared with cultivated A. officinalis. All shoots were screened for saponins by LC-MS, and in vitro antiproliferative activities against the HT-29 colorectal cancer cell line (by MTT assay). The total saponins (TS) contained in the crude extracts ranged from 710.0 (A. officinalis) to 1258.6 mg/100 g dw (A. acutifolius). It stands out the richness of compounds detected in this work: a total of 47 saponins have been detected and quantified in the edible parts (shoots) of 5 taxa of Asparagus. The structure of all the saponins found present skeletons of the furostane and spirostane type. In turn, the structures with a furostane skeleton are divided into unsaturated and dioxygenated, both in the 20-22 position. The sum of dioscin and derivatives varied largely along the studied taxa. It reached the following percentages of TS: 27.11 (A. officinalis), 18.96 (A. aphyllus), 5.37 (A. acutifolius), and 0.59 (A. albus), while in A. horridus such compound remains undetected. Aspachiosde A, D, and M varied largely among samples, while a total of seven aspaspirostanosides were characterized in the analyzed species. Hierarchical cluster analysis of the saponin profiles clearly separated the various taxa and demonstrated that the taxonomic position is more important than the place from which the samples were acquired. Thus, saponin profiles have chemotaxonomic significance in Asparagus taxa. The MTT assay showed dose- and time-dependent inhibitory effects of several saponins extracts on HT-29 cancer cells, standing out the cell growth inhibition exercised by A. albus and A. acutifolius (GI50 of 125 and 175 µg/mL). This work constitutes a whole approach to evaluate the saponins from shoots of different Asparagus taxa and provide arguments for use them as functional foods.

Pyrethroid pesticides (PYRs) as the third most widely used pesticides, following organophosphorus and carbamate pesticides, which are of significant importance in the analysis and detection of vegetables. However, the current pretreatment technology for PYRs confronts challenges of difficult separation and low enrichment efficiency, resulting in a cumbersome and time-consuming pretreatment process with poor selectivity. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed to simultaneously purify and enrich five PYRs in vegetables, with the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. The COF-SiO2@Fe3O4 was prepared by a simple solvothermal conditions method, using Fe3O4 as magnetic core, benzidine and 3,3,5,5-tetraaldehyde biphenyl as two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on extraction efficiency was investigated to optimize the MSPE conditions, including adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00–100 μg·kg-1 (1.00–100 μg·kg-1 for bifenthrin and 2.5–100 μg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3–1.5 μg·kg-1, and the limits of quantification (LOQs) were 0.9–4.5 μg·kg-1. The recoveries were 80.2–116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promising prospects for the determination of PYRs in real samples.

Due to its large hole mobility, Organic Rubrene (C42H28) has attracted research questions on its applications in electronic devices. In this work, extensive first-principles calculations were made to predict some temperature and doping dependent properties of Organic Semi- conductor Rubrene. We use Density Functional Theory (DFT) to investigate the electronic structure, elastic and transport properties of the Orthorhombic phase of the Rubrene compound. The calcu- lated band structure shows the Orthorhombic phase has a direct bandgap of 1.26 eV. From the Vickers hardness (1.080 GPa), our calculations show that Orthorhombic Rubrene is not a super hard material and can find useful application as a flexible semicon- ductor. The calculated transport Inverse Effective Mass and Elec- tronic Fitness Function show that the Orthorhombic Rubrene Crystal Structure is a p-type thermoelectric material at high temperatures.

Objective. To test the hypothesis that a session of unilateral tSMS over the dominant primary motor cortex (M1) in healthy subjects produces a transient decrease in manual dexterity. Methods. A triple-blinded randomized control trial was conducted in 40 healthy participants who were allocated to real- or sham-tSMS group. Each participant underwent one session of tSMS and were assessed before, immediately after, 15 minutes, and 40 minutes after stimulation. Outcome measures were Finger Tapping Test (FTT), 5-seconds FTT, nine Hole Peg Test, and the hand grip assessment. Results: Significant differences were found between groups 15 minutes after stimulation in favor of the tSMS group in the FTT (2.2 ± 0.99; CI= .18-4.22; d= .84p=.034), and 5-second FTT (4.2 ± 1.98; CI= .199-8.2, d= .68; p=.04). In the intragroup analysis, a significantly lower number of taps 15 minutes after stimulation was observed in sham group (3.3 ± 1.01; CI= .47-6.13; d= .42; p=.015), but not in the real stimulation group. Conclusion: A unilateral session of tSMS in the M1 of the dominant hemisphere of healthy individuals does not reduce manual dexterity or grip strength. This technique could have benefits on the motor performance of the arm contralateral to the stimulated motor cortex

Based on screening in computational biology and biological in vitro assays, five natural products isolated from extracts of the herbal medicine toad skin, such as cinobufagin (CBFi), bufalin (BFi), arenobufagin (ABFi), telocinobufagin (TBFi), bufotalin (BFTi), were subjected to molecular docking calculations with the use of SARS-CoV-2 main protease (PDB 6LU7 and 7BTF) and top-scoring ligand-receptor complexes were obtained. The results showed that the binding energy of ABFi to the 3CL protein was -17.044kcal/mol, which was higher than CBFi and TBFi. However, the binding energy of ABFi to the RdRp protease was -23.250 kcal/mol, which was much lower than that of CBFi and TBFi, EVEN lower than that of ABFi to the 3CL protein. ABFi also has polar interactions with amino acids such as Glu811, Ser814, Ser681 and Thr680 of RdRp enzyme. The results revealed that ABFi had a moderate inhibitory effect on the cell proliferation of SARS-CoV-2 in vitro, with an inhibition rate of 61.12%, even weaker than Remdesivir. This new discovery provides us with new ideas for in-depth studies on the development of natural products with this class of structural generalizations as inhibitors of SARS-CoV-2, and provides an experimental basis for the next step of mechanistic studies.

This study investigates the possibility of using machine learning models created in DeepLabCut and Create ML to automate aspects of behavioral coding and aid in behavioral analysis. Two models with different capabilities and complexities were constructed and compared to a manually observed control period. The accuracy of the models was assessed before being applied to 7 nights of footage of the nocturnal behavior of two African elephants (Loxodonta africana). The resulting data was used to draw conclusions regarding behavioral differences between the two elephants and between individually observed nights, thus proving that such models can aid researchers in be-havioral analysis. The models were capable of tracking simple behaviors with high accuracy, but had certain limitations regarding detection of complex behaviors, such as the stereotyped behavior sway, and displayed confusion when deciding between visually similar behaviors. Further expansion of such models may be desired to create a more capable aid with the possibility of automating behavioral coding.

Background We investigated to determine the effectiveness of verbal feedback in learning the round-off back somersault on the balance beam with stable landing. Methods: The research material consisted of female gymnasts (n = 16). They were randomly assigned to one of two groups: FKE group (n = 8) with feedback on key elements, or FAE group (n = 8) with 100% feedback on all errors made in the phase structure of the task. Results: Based on research, it was established that key elements could be identified in the preparatory, main and final phases. Mixed ANOVA showed that significant differences (p &lt; 0.05) were noted due to the teaching method used (Group x Time factor) when performing the gymnastic routine of round-off back somersault with stable landing on the balance beam. Based on the Welch t test for independent data it was revealed that the group with feedback on the key elements obtained significantly higher mean scores from judges at the end of the experiment. Conclusions: The findings of the present study point to a possibility of offering coaches teaching methods that increase the effectiveness of learning complex motor skills and indicate a possibility of applying such solutions in groups of female gymnasts both in training and during competitions.

Triazole derivatives of fluorescein containing N,N-dimethylaminopropyl fragments and their ammonium salts were synthesized with yields of 74 - 85%. The resulting compounds exhibit fluorescent properties in the green region of the visible spectrum. The critical aggregation concentration (CAC) was estimated using a py-rene fluorescent probe corresponding to a range of 0.28 - 1.43 mM, and at concentrations above the CAC the compounds form stable aggregates ranging from 165 to 202 nm. A relative quantum yield of 5-24% has been calculated based on fluorescence and UV spectra. The best value is shown by a derivative containing a tetradecyl substituent. When studying the photocatalytic properties of synthesized compounds through the reaction between N-substituted 1,2,3,4-tetrahydroisoquinoline and malonic ester, the mono-tetradecyl deriva-tive demonstrated the best results. According to gas chromatography-mass spectrometry (GC-MS) data, the conversion of the initial heterocycle reached 95%. Therefore, these resulting compounds have the potential to act as an effective photocatalysts.