Nitride Spinel: An Ultraincompressible High‐Pressure Form of BeP2N4

Owing to its outstanding elastic properties, the nitride spinel γ‐Si₃N₄ is of considered interest for materials scientists and chemists. DFT calculations suggest that Si₃N₄‐analog beryllium phosphorus nitride BeP₂N₄ adopts the spinel structure at elevated pressures as well and shows outstanding elastic properties. Herein, we investigate phenakite‐type BeP₂N₄ by single‐crystal synchrotron X‐ray diffraction and report the phase transition into the spinel‐type phase at 47 GPa and 1800 K in a laser‐heated diamond anvil cell. The structure of spinel‐type BeP₂N₄ was refined from pressure‐dependent in situ synchrotron powder X‐ray diffraction measurements down to ambient pressure, which proves spinel‐type BeP₂N₄ a quenchable and metastable phase at ambient conditions. Its isothermal bulk modulus was determined to 325(8) GPa from equation of state, which indicates that spinel‐type BeP₂N₄ is an ultraincompressible material.     

SO 2 sorption properties of fly ash zeolites

In the presented study, the sulfur dioxide sorption properties of fly ash zeolite X were investigated. Sorption tests were performed on fly ash zeolite samples that were not prepared specially for sorption, in addition to dried samples and samples in the presence of water vapor. The samples saturated with water vapor showed the highest sorption capacity. The sorption capacity of the samples additionally dried prior to the sorption experiment was higher than that of the samples that were not specially prepared for the sorption test. Regeneration tests indicated relatively good regeneration properties. The obtained results were described with the use of Langmuir, Sips, and Dubinin–Astakhov models, with the Dubinin–Astakhov model providing the best fit.     

Molecular Targets Implicated in the Antiparasitic and Anti-Inflammatory Activity of the Phytochemical Curcumin in Trichomoniasis

Trichomoniasis, is the most prevalent non-viral sexually transmitted disease worldwide. Although metronidazole (MDZ) is the recommended treatment, several strains of the parasite are resistant to MDZ, and new treatments are required. Curcumin (CUR) is a polyphenol with anti-inflammatory, antioxidant and antiparasitic properties. In this study, we evaluated the effects of CUR on two biochemical targets: on proteolytic activity and hydrogenosomal metabolism in Trichomonas vaginalis. We also investigated the role of CUR on pro-inflammatory responses induced in RAW 264.7 phagocytic cells by parasite proteinases on pro-inflammatory mediators such as the nitric oxide (NO), tumor necrosis factor α (TNFα), interleukin-1beta (IL-1β), chaperone heat shock protein 70 (Hsp70) and glucocorticoid receptor (mGR). CUR inhibited the growth of T. vaginalis trophozoites, with an IC₅₀ value between 117 ± 7 μM and 173 ± 15 μM, depending on the culture phase. CUR increased pyruvate:ferredoxin oxidoreductase (PfoD), hydrogenosomal enzyme expression and inhibited the proteolytic activity of parasite proteinases. CUR also inhibited NO production and decreased the expression of pro-inflammatory mediators in macrophages. The findings demonstrate the potential usefulness of CUR as an antiparasitic and anti-inflammatory treatment for trichomoniasis. It could be used to control the disease and mitigate the associated immunopathogenic effects.     

Proteomic Profiling of the Human Fetal Multipotent Mesenchymal Stromal Cells Secretome

Secretome of multipotent mesenchymal stromal cells (MSCs) is actively used in biomedical applications such as alveolar bone regeneration, treatment of cardiovascular disease, and neurodegenerative disorders. Nevertheless, hMSCs have low proliferative potential and production of the industrial quantity of their secretome might be challenging. Human fetal multipotent mesenchymal stromal cells (FetMSCs) isolated from early human embryo bone marrow are easy to expand and might be a potential source for pharmaceutical substances production based on their secretome. However, the secretome of FetMSCs was not previously analyzed. Here, we describe the secretome of FetMSCs using LC-MALDI shotgun proteomics. We identified 236 proteins. Functional annotation of the identified proteins revealed their involvement in angiogenesis, ossification, regulation of apoptosis, and immune response processes, which made it promising for biomedical applications. The proteins identified in the FetMSCs secretome are involved in the same biological processes as proteins from previously described adult hMSCs secretomes. Nevertheless, many of the common hMSCs secretome components (such as VEGF, FGF, Wnt and TGF-β) have not been identified in the FetMSCs secretome.     

Probing the Roughness of Porphyrin Thin Films with X-ray Photoelectron Spectroscopy

Thin-film growth of molecular systems is of interest for many applications, such as for instance organic electronics. In this study, we demonstrate how X-ray photoelectron spectroscopy (XPS) can be used to study the growth behavior of such molecular systems. In XPS, coverages are often calculated assuming a uniform thickness across a surface. This results in an error for rough films, and the magnitude of this error depends on the kinetic energy of the photoelectrons analyzed. We have used this kinetic-energy dependency to estimate the roughnesses of thin porphyrin films grown on rutile TiO₂(110). We used two different molecules: cobalt (II) monocarboxyphenyl-10,15,20-triphenylporphyrin (CoMCTPP), with carboxylic-acid anchor groups, and cobalt (II) tetraphenylporphyrin (CoTPP), without anchor groups. We find CoMCTPP to grow as rough films at room temperature across the studied coverage range, whereas for CoTPP the first two layers remain smooth and even; depositing additional CoTPP results in rough films. Although, XPS is not a common technique for measuring roughness, it is fast and provides information of both roughness and thickness in one measurement.     

Interactions between a dsDNA Oligonucleotide and Imidazolium Chloride Ionic Liquids: Effect of Alkyl Chain Length,Part I

Ionic liquids (ILs) have become nearly ubiquitous solvents and their interactions with biomolecules has been a focus of study. Here, we used the fluorescence emission of DAPI, a groove binding fluorophore, coupled with molecular dynamics (MD) simulations to report on interactions between imidazolium chloride ([Im_n,1]⁺) ionic liquids and a synthetic DNA oligonucleotide composed entirely of T/A bases (7(TA)) to elucidate the effects ILs on a model DNA duplex. Spectral shifts on the order of 500–1000 cm⁻¹, spectral broadening (~1000 cm⁻¹), and excitation and emission intensity ratio changes combine to give evidence of an increased DAPI environment heterogeneity on added IL. Fluorescence lifetimes for DAPI/IL solutions yielded two time constants 0.15 ns (~80% to 60% contribution) and 2.36–2.71 ns for IL up to 250 mM. With DNA, three time constants were required that varied with added IL (0.33–0.15 ns (1–58% contribution), ~1.7–1.0 ns (~5% contribution), and 3.8–3.6 ns (94–39% contribution)). MD radial distribution functions revealed that π-π stacking interactions between the imidazolium ring were dominant at lower IL concentration and that electrostatic and hydrophobic interactions become more prominent as IL concentration increased. Alkyl chain alignment with DNA and IL-IL interactions also varied with IL. Collectively, our data showed that, at low IL concentration, IL was primarily bound to the DNA minor groove and with increased IL concentration the phosphate regions and major groove binding sites were also important contributors to the complete set of IL-DNA duplex interactions.     

Structural Diversity of Silver Fluorinated β-Diketonates: Effect of the Terminal Substituent and Solvent

In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with β-diketonate ligands (R¹C(O)C_αHC(O)R²)⁻ we synthesized a series of the compounds containing tfac- (R₁ = CH₃, R² = CF₃) and pfpac- (R₁ = CH₃, R² = C₂F₅) anions. Solvent-free [Ag(L)]_∞ (L = tfac 1, pfpac 2) compounds and the corresponding acetonitrile and toluene adducts have been characterized by elemental analysis and/or NMR, IR and single-crystal XRD. This series includes five new coordination polymers. Compound 1 is a 3D coordination framework based on Ag–O_{chelate/bridge}, Ag–C_α bonds, and argentophilic interactions. An increase in the fluorinated group leads to a chain coordination polymer 2 of an unusual structural organization. These chains can be represented as a “DNA-type”, where two intertwined helices based on Ag–O_chelate and Ag–C_α bonds are connected through Ag–O_bridge ones. Two structural types of chain coordination polymers, [Ag(tfac)(CH₃CN)] and [Ag₂(L)₂(solvent)], have been revealed for the adducts. The latter structural type differs significantly from the previously studied toluene and acetonitrile adducts of fluorinated Ag(I) β-diketonates of the same stoichiometry. Thermal analysis in helium showed that both 1 and 2 decompose to metallic silver with the compound of pfpac-ligand being slightly more stable.     

The Theoretical and Experimental Investigation of the Fluorinated Palladium β-Diketonate Derivatives: Structure and Physicochemical Properties

To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH₃CXCHCO(R))₂] with β-diketone [tfa−1,1,1-trifluoro-2,4-pentanedionato (1); pfpa−5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba−5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and β-iminoketone [i-tfa−1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa−5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (4); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato (6)] ligands were synthesized with 70–80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd β-diketonates contained both cis and trans isomers, while only trans isomers were detected in the solutions of Pd β-iminoketonates. The molecules 2–6 and new polymorphs of complexes 3 and 5 were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands. The H…F contacts were the main ones involved in the formation of packages of molecules 1–2, and C…F, F…F, NH…F contacts appeared in the structures of complexes 4–6. The stability of complexes and their polymorphs in the crystal phases were estimated from DFT calculations. The TG data showed that the volatility differences between Pd β-iminoketonates and Pd β-diketonates were minimized with the elongation of the fluorine chain in the ligands.     

Biological Activity of Extracts of Red and Yellow Fruits of Cornus mas L.—An In Vitro Evaluation of Antioxidant Activity,Inhibitory Activity against α-Glucosidase,Acetylcholinesterase, and Binding Capacity to Human Serum Albumin

Although extracts are broadly used in order to support the treatment of numerous diseases, only in a limited number of cases is the process of applying and establishing their mechanisms of action scientifically analyzed. Fruits of Cornelian cherry are an abundant source of iridoids, anthocyanins, flavonols and phenolic acids. The aim of the present study was to evaluate the in vitro bioactivity of red and yellow Cornelian cherry fruits’ extracts. The biological potential of extracts, in a broad sense, involved antioxidant activity in relation to phosphatidylcholine liposomes, inhibitory ability against α-glucosidase and acetylcholinesterase enzymes, as well as interactions with human serum albumin. Studies showed that both extracts were more effective in protecting liposome membranes against free radicals produced by AAPH in an aqueous environment due to the fact that they can be better eliminated by the hydrophilic components of the extracts than those produced by UVB radiation. Extracts exhibited inhibitory activity against acetylcholinesterase and α-glucosidase, wherein loganic acid extract showed noncompetitive inhibition of the enzyme. Moreover, extracts binded to albumin mainly through hydrogen bonds and van der Waals forces. Taken together, red and yellow cherry fruits’ extracts exhibit diverse biological properties and can be exploited as a source of natural therapeutic agents.     

Effects of Regioisomerism on the Antiproliferative Activity of Hydroxystearic Acids on Human Cancer Cell Lines

A series of regioisomers of the hydroxystearic acid (HSA) was prepared, and the effect of the position of the hydroxyl group along the chain on a panel of human cancer cell lines was investigated. Among the various regioisomers, those carrying the hydroxyl at positions 5, 7, and 9 had growth inhibitor activity against various human tumor cell lines, including CaCo-2, HT29, HeLa, MCF7, PC3, and NLF cells. 10-HSA and 11-HSA showed a very weak effect. 8-HSA did not show inhibitory activity in all cell lines. The biological role of 7-HSA and 9-HSA is widely recognized, while little is known about the effects of 5-HSA. Therefore, the biological effects of 5-HSA in HeLa, HT29, MCF7, and NLF cell lines were investigated using the Livecyte’s ptychography technology, which allows correlating changes in proliferation, motility, and morphology as a function of treatment at the same time. 5-HSA not only reduces cell proliferation but also induces changes in cell displacement, directionality, and speed. It is important to characterize the biological effects of 5-HSA, this molecule being an important component of fatty acyl esters of hydroxy fatty acids (FAHFA), a class of endogenous mammalian lipids with noticeable anti-diabetic and anti-inflammatory effects.