Search Results (144)

Background/Objectives: Recent data on long-term consequences of prematurity on bone health are conflicting. The aim of this study was to assess the metabolic bone profile and bone mineral density (BMD) in prepubertal children born prematurely and to examine possible associations between bone health parameters and perinatal morbidity factors. Methods: This cross-sectional observational study included 144 children of mean (SD) age 10.9 (1.6) years: 49 children born very preterm (≤32 gestational weeks), 37 moderate-to-late preterm (32⁺¹ to 36⁺⁶ gestational weeks), and 58 born at term (controls). Serum levels of calcium/Ca, phosphorus/P, alkaline phosphatase/ALP, 25-hydroxyvitamin D/25(OH)D, bone formation markers (osteocalcin/OC, procollagen type I C-terminal propeptide/PICP, and insulin growth factor-1/IGF-1), and bone resorption markers (serum tartrate-resistant acid phosphatase 5b/bone TRAP5band urinary calcium-to-creatinine ratio) were measured. Total-body and lumbar-spine BMD and BMD Z-scores were calculated using dual-energy X-ray absorptiometry/DXA. Results: Children born very preterm showed significantly higher ALP, OC, PICP, and bone TRAP5b levels compared to controls, as well as compared to children born moderate-to-late preterm. Total-body and lumbar-spine BMD Z-scores were significantly lower in the very preterm-born group compared to controls. Gestational diabetes, preeclampsia, and bronchopulmonary dysplasia were associated with lower total-body BMD in the very preterm-born population. Conclusions: Preterm birth is associated with impaired metabolic bone profile and lower total-body and lumbar-spine BMD in childhood. Moderate-to-late preterm-born children exhibit altered metabolic bone parameters compared to very preterm-born children. Further research in children might allow better insight into the long-term impact of preterm birth on bone health. Full article

The kinetics of the depolymerization of natural rubber (NR) to hydroxyl-terminated natural rubber (HTNR) by hydrogen peroxide (H₂O₂) in the presence of a Fenton catalyst within an acidic milieu and under ultraviolet radiation has been rigorously examined utilizing infrared spectroscopy to determine the alterations in molar mass and the functional characteristics. The kinetic model was analyzed in accordance with the elementary reaction, encompassing the following mechanisms: the interaction between hydroxyl radicals and NR, producing radical NR and hydroxylated NR; the reaction wherein radical NR and hydroxyl radicals yield hydroxylated NR; and the subsequent reaction of hydroxylated NR with hydroxyl radicals producing lower radical NR, hydroxylated terminated NR, radical NR, and hydroxylated NR. The conversion of the NR polymer and the total hydroxyl content were discerned at the absorption bands of the CH₂-CH₂ and OH groups located at 850 cm⁻¹ and 3400 cm⁻¹, respectively. The absorption peak at 1850 cm⁻¹ attributed to CH₃ was employed as the reference group for calibration. The influence of the temperature on the depolymerization process conformed to the Arrhenius equation, characterized by activation energies of 750 K and 1200 K. The impact of the H₂O₂/Fenton ratio on the depolymerization process follows a power law with power coefficients of 1.97 and 1.82. Full article

Significant heavy metals contamination is often caused by rapid industrialization, which is devastating to both public health and the environment. Conventional processes of metal removal also result in the accumulation of secondary waste. This work proposes the use of a novel fungal biomass (microwave heat dried) from Arthrinium malaysianum for the biosorption of toxic chromium. We have meticulously explored and investigated the interactions of hexavalent chromium with dried biomass using several cutting-edge techniques like FTIR for studying the involvement of functional groups on the biomass surface, XRD for the surface architecture changes after metal binding, XPS to unravel the reduction of hexavalent chromium into its non-toxic form, and FESEM-EDX for the visualization of the ultra-structure of fungal cell surface. The Langmuir isotherm demonstrates that the maximum removal capacity Q_max of Cr(VI) is 102.310 mgg⁻¹, at a pH of 3.5 with 100% removal of Cr(VI). There were substantial changes in the surface architecture during adsorption, confirmed by FESEM and AFM studies. FTIR and XPS data analysis indicated that carbonyl, hydroxyl, phosphate, and amine groups were responsible for the conversion of Cr(VI) (toxic) to Cr(III) (non-toxic). The IR spectra of biomass treated with Cr showed a decreased C-O stretching intensity and slight shriveling of the -OH band, and the bands in the FTIR spectra at 1642 cm⁻¹ to 1635 cm⁻¹ and at 1549 cm⁻¹ to 1547 cm⁻¹ shifted and appeared quite distinct. XRD revealed that the chromium-treated biomass had greater crystalline features and also the appearance of a wide peak where 2θ = 20°, approximately, indicating an amorphous nature at 576.0 eV and in highly loaded chromium (500 mg/L) biomass, with the Cr2p level displaying a slight shift, eventually terminating in a (576.0 eV) Cr₂O₃ to Cr(III) peak. Since the FTIR and XPS data obtained revealed that Cr(VI) reduces to Cr(III), this fungal biomass can also be used for generating metallic nanoparticles during biosorption. Thus, we suggest that the above-mentioned fungal biomass could be a very useful biomaterial for future translational research. We are in the process of fabricating beads with powdered biomass for further studies. Full article

For the interaction of angiotensin II (AngII) with AngII type 1 receptors (AT₁R), two potential proton hopping pathways have been identified, each associated with distinct physiological outcomes. The octapeptide AngII (Asp¹-Arg²-Val³-Tyr⁴-Ile⁵-His⁶-Pro⁷-Phe⁸) appears to form a charge relay system (CRS) in solution in which the C-terminal carboxylate abstracts a proton from the His⁶ imidazole group, which, in turn, abstracts a proton from the Tyr⁴ hydroxyl (OH) group, creating a tyrosinate anion. When AngII binds to the AT₁R, the CRS can be reconstituted with D281 of the receptor taking up the role of the Phe⁸ carboxylate in the tripartite interaction, whilst the Phe⁸ carboxylate forms a salt bridge with K199 of the receptor. As a consequence, the Tyr⁴ OH of AngII is positioned with accessibility to either the Phe⁸ carboxylate (bound to K199) or the His⁶ imidazole (activated by D281), thereby creating a potential gating mechanism for AT₁R receptor signaling. This study summarizes evidence based on structure activity data for various analogs wherein Tyr⁴ OH interaction with His⁶ imidazole (CRS formation) leads to G protein sequestration and vasoconstriction, whereas Tyr⁴ OH interaction with Phe⁸ carboxylate (bound to K199) engenders arrestin-mediated vasodilation and receptor desensitization. These findings, combined with quantum mechanical (semiempirical) calculations of CRS proton transfer presented herein, provide insights for the therapeutic targeting of angiotensin receptor blockers (sartans) and the development of second-generation drugs (bisartans). Full article

Peptoids are peptidomimetics in which the side chain is attached to the nitrogen of the amide group rather than the α-carbon. This alteration in the backbone structure is highly valued because it endows beneficial properties, including enhanced resistance to proteolysis, greater immunogenicity, improved biostability, and superior bioavailability. In this current study, we focused on the Ugi-4CR-based one-pot synthesis of peptoids using 1,4-dithiane-2,5-diol as the carbonyl component together with amine, carboxylic acid, and isocyanides. Four new peptoids—5a, 5b, 5c, and 5d—were designed and efficiently prepared in good chemical yields and were subjected to DFT investigations for their electronic behavior. These compounds have free OH, SH, and terminal triple bonds for further chemistry. In a computational analysis, the spectral data of compounds 5a–5d were juxtaposed with calculated spectral values derived from the B3LYP/6-311G(d,p) level. The electronic excitation and orbital contributions of 5a–5d were predicted using TD-DFT calculations. A natural bond order (NBO) analysis was utilized to investigate the electronic transition of newly synthesized peptoids, focusing on their charge distribution patterns. Furthermore, MEP and NPA analyses were conducted to predict charge distribution in these compounds. The reactivity and stability of the targeted peptoids were evaluated by global reactivity descriptors, which were determined with frontier molecular orbital analysis. The DFT results revealed that compound 5c displayed marginally higher reactivity compared to 5a, 5b, and 5d, possibly due to its extended conjugation. Full article

Objectives: The aim of this observational study was to evaluate whether the presence of periapical inflammatory cysts (PIC) is accompanied by a state of vitamin D (25OHD) 25(OH)D insufficiency or deficiency and biochemical variations in biomarkers of bone metabolism such as osteocalcin (OC), isoenzyme of bone alkaline phosphatase (BALP), and C-terminal telopeptide of type 1 collagen (CTX). Methods: A total of 56 patients (group P), 36 males and 20 females, of which 42 had one cyst (group P1) and 14 had multiple periapical cysts (group P2), alongside 56 healthy subjects (group H) were recruited. Rx-OPT and clinical evaluation were used to evaluate the presence of PIC. At the first visit, all subjects underwent venous sampling (group P and H) to measure bone biomarkers by the chemiluminescence method. The Mann–Whitney test was used to compare the different biomarkers in the H vs. P, H vs. P1, H vs. P2, and P1 vs. P2 groups. The Mann–Whitney test was used to compare biomarker levels between the study groups. ROC curves were used to search for the concentration of the different biomarkers in which the best sensitivity and specificity were found. Results: 25OHD and CTX showed a difference between H vs. P, H vs. P1, H vs. P2, and P1 vs. P1 groups (p < 0.05). The study of the ROC curves with a comparison between concentrations in the H vs. P group showed the best sensitivity and specificity for 25OHD at a concentration <19 ng/mL, highlighting a picture of 25OHD deficiency. Conclusions: The presence of apical cysts could be indicative of a vitamin D deficiency that should be appropriately treated. The findings suggest that vitamin D deficiency, given its role in bone metabolism and mineralisation, may contribute to a biological environment that favours the development or persistence of periapical cystic lesions. Full article

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture in MeOH gave complex [Co^III₂Fe^III(NH₂pao)₆](ClO₄)₂(NO₃) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co^III₂Fe^III(NH₂pao)₆]³⁺ which are strictly linear by symmetry. The central high-spin Fe^III ion is connected to each of the terminal low-spin Co^III ions through the oximato groups of three 2.1110 (Harris notation) NH₂pao⁻ ligands, in such a way that the six O atoms are bonded to the octahedral Fe^III center ({Fe^IIIO₆} coordination sphere). Each terminal octahedral Co^III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH₂pao⁻ groups ({Co^IIIN₆} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO₄⁻ and NO₃⁻ counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d⁶ cobalt(III) and a charge-transfer NH₂pao⁻ → Fe^III band. The δ and ΔΕ_Q ⁵⁷Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe^III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe^III. A critical discussion of the importance of NH₂paoH and its anionic forms (NH₂pao⁻, NHpao²⁻) in homo- and heterometallic chemistry is also attempted. Full article

Five new coordination compounds that included three coordination polymers and two supramolecular complexes were obtained by reactions of different cadmium salts (tetrafluoroborate, nitrate, and perchlorate) with dianiline chromophores, 4,4′-diaminodiphenylmethane (ddpm), and 4,4′-diaminodiphenylethane (ddpe). The crystal structures were studied by single-crystal X-ray analysis. The coordination arrays with the ddpm chromophore included {[Cd(OH)(H₂O)(ddpm)₂](BF₄)}_n (1) as a one-dimensional (1D) coordination garland chain, {[Cd(NO₃)(ddpm)₂](H₂O)(NO₃)}_n (2) as a two-dimensional (2D) coordination layer, and [Cd(bpy)₂(ddpm)₂](ddpm)(NO₃)₂ (3) as a supramolecular complex. The products with the ddpe chromophore were identified as {[Cd(phen)₂(ddpe)](ClO₄)₂}_n (4) in the form of a linear coordination chain and [Cd(phen)₃](ClO₄)₂(ddpe)_0.5(CH₃CN)_0.5 (5) as a supramolecular complex. The extension of coordination arrays in 1, 2, and 4 was achieved via dianiline ligands as bidentate linkers and additionally via bridging of nitrate anions in 2. The diversification of products became possible due to usage of 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) as co-ligands forming the terminal corner fragments [Cd(bpy)₂]²⁺, [Cd(phen)₂]²⁺, and [Cd(phen)₃]²⁺ in 3–5, respectively. The assembling of coordination entities occurred via the interplay of hydrogen bonds with the participation of amino groups, water molecules, and inorganic anions. Two dianilines were powerful luminophores in the crystalline phase, while the photoluminescence in 1–5 was considerably weaker than in the pure ddpm and ddpe luminophores and redistributed along the spectrum. Full article

In an earlier report, we conjectured that oligo-phenylenevinylene (OPV) molecules bearing terminal OH groups may form molecular complexes in organogels prepared in benzyl alcohol. This assumption was based on circumstantial evidence only. In this paper, we report on new experimental evidence by means of neutron diffraction that unambiguously demonstrates this conjecture. After ascertaining that the thermodynamic properties of OPV gels are not altered by the use of a solvent isotope (hydrogenous vs. deuterated benzyl alcohol), we show that the neutron diffraction pattern in hydrogenous benzyl alcohol differs from that in deuterated benzyl alcohol. These patterns also exhibit additional peaks with respect to those obtained by X-ray. Comparison is further achieved with an OPV molecule without hydrogen bond terminal groups. In the latter case, no molecular complex is formed. These molecular structures may have a direct bearing on the differences observed in the gel morphologies. Full article

MXenes, a groundbreaking class of two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides, have emerged as highly promising materials for photocatalytic applications due to their unique structural, electrical, and surface properties. These materials are synthesized by selectively etching the A layer from MAX phases, yielding compositions with the general formula M_n+1X_nT_x, where M is a transition metal, X represents carbon or nitrogen, and T_x refers to surface terminations such as ^–OH, ^–O, or ^–F. This review delves into the advanced synthesis techniques of MXenes, including fluoride-free etching and molten salt methods, and explores their potential in photocatalysis for environmental remediation. MXenes exhibit remarkable light absorption capabilities and efficient charge carrier separation, making them highly effective for the photocatalytic degradation of organic pollutants under visible light. Modulating their surface chemistry and bandgap via functional group modifications further enhances their photocatalytic performance. These attributes position MXenes as next-generation materials for sustainable photocatalytic applications, offering significant potential in addressing global environmental challenges. Full article

The interfacial properties of blends play a crucial role in determining the mechanical characteristics of polyamide alloys. This study focused on the preparation of PA6/PBS alloys via a melt blending method, utilizing 3-aminopropyltriethoxysilane (KH550) as the compatibilizer to examine the impact of KH550 on the interfacial and mechanical properties of these binary blends. The results demonstrated that the amino groups in KH550 reacted with the terminal carboxyl groups in polyamide 6 (PA6) and the B-OH in polyborosiloxane (PBS), which significantly enhanced interfacial adhesion between the two phases. A reduction in the particle size and interparticle distance of PBS particles was related to increased interfacial adhesion within the blends. The superior dispersion and robust interfacial adhesion caused a notable improvement in the notched Izod impact strength, rising from 7.9 kJ/m² to 29.7 kJ/m² at 25 °C and from 6.3 kJ/m² to 16.6 kJ/m² at −50 °C. Consequently, KH550 proved to be an effective toughening agent for the PA6/PBS system. Furthermore, the PA6/PBS blends containing a high content of KH550 induced a morphological transformation from a “sea-island” structure to a partially interpenetrating polymer network, leading to the absence of a double-yield phenomenon in the tensile curve. Full article

A series of triphenylene (TP) compounds—denoted 3,6-THTP-DiCnOH—bearing four hexyloxy ancillary chains and two variable-length alkoxy chains terminally functionalized with hydroxyl groups have been synthesized and characterized. The shorter homologs revealed mesogenic characteristics, giving rise to thermotropic mesophases in which π-stacked columns of H-bound dimers self-organize yielding superstructures. Molecular-scale models are proposed to account for their structural features. The three studied compounds yielded supramolecular gels in methanol; their ability to gelify higher alcohols was found to be enhanced by the presence of water. The intermediate homolog also gelled n-hexane. Compared to their isomeric 2,7-THTP-DiCnOH analogs, the 3,6-derivatives showed a higher tendency to give rise to LC phases (wider thermal ranges) and a lower organogelling ability (variety of gelled solvents, lower gels stabilities). The overall results are analyzed in terms of different kinds of competing H-bonds: intramolecular, face-to-face dimeric, lateral polymeric, and solvent–TP interactions. Full article

Zheshengite (IMA2022-011), Pb₄ZnZn₂(AsO₄)₂(PO₄)₂(OH)₂, is a new mineral from Sanguozhuang Village in the eastern Dongchuan Copper Ore Field, Yunnan Province, China. The new mineral is named after Zhesheng Ma (1937–). Zheshengite occurs as prismatic single crystals with chisel-like terminations on hemimorphite, with crystal sizes ranging from 0.02 to 0.05 mm. It is a brittle mineral with irregular fractures, a Mohs hardness of 2½ to 3, perfect cleavage on {011}, and a calculated density of 6.26 g/cm³. The empirical formula of zheshengite, based on 18 O atoms per formula unit, is (Pb_4.12Ca_0.01)_∑4.13(Zn_0.83Cu_0.23Fe_0.04)_∑1.10Zn_2.00[(As_0.90P_0.10)_∑1.00O₄]₂[(P_0.94Si_0.01)_∑0.95O₄]₂(OH)₂. Zheshengite exhibits a triclinic structure (space group P−1, no. 2), with unit-cell parameters: a = 4.7746(4) Å, b = 8.4920 (7) Å, c = 10.4056 (8) Å, α = 97.087 (7)°, β = 101.060 (7)°, γ = 92.996 (7)°, V = 409.66 (6) ų, and Z = 1. As a member of the dongchuanite group, zheshengite features a dongchuanite-type structure. This study reveals the impact of As–P isomorphic substitution on unit-cell parameters in the dongchuanite group, identifying correlations between As content and changes in parameters a and V, which may serve as diagnostic indicators for dongchuanite group minerals. In addition, the structure studies of zheshengite may have implications for environmental protection. Full article

Ovarian cancer (OC) must be detected in its early stages when the mortality rate is the lowest to provide patients with the best chance of survival. Lysophosphatidic acid (LPA) is a critical OC biomarker since its levels are elevated across all stages and increase with disease progression. This paper presents an LPA assay based on a thickness shear mode acoustic sensor with dissipation monitoring that involves a new thiol molecule 3-(2-mercaptoethanoxy)propanoic acid (HS-MEG-COOH). HS-MEG-COOH is an antifouling linker that provides (a) antifouling properties for gold substrates and (b) linking ability via its terminal carboxylic acid functional group. The antifouling ability of HS-MEG-COOH was tested in whole human serum. The new molecule was applied to the LPA assay in conjunction with a spacer molecule, 2-(2-mercaptoethoxy)ethan-1-ol (HS-MEG-OH), in a 1:1 v/v ratio. HS-MEG-COOH was covalently linked to gelsolin–actin, a protein complex probe that dissociates due to LPA-binding. LPA was detected in phosphate-buffered saline and undiluted human serum and achieved a low limit of detection (1.0 and 0.7 μM, respectively) which was below the concentration of LPA in healthy individuals. The antifouling properties of HS-MEG-COOH and the detection of LPA demonstrate the ability of the sensor to successfully identify the early-stage OC biomarker in undiluted human serum. Full article

The scope of this work was to develop a thin-film composite (TFC) membrane for the separation of CO₂/CO mixtures, which are relevant for many processes of gas processing and gasification of carbon-based feedstock. Special attention was given to the development of highly permeable porous polysulfone (PSF) supports (more than 26,000 GPU for CO₂) since both the selective and support layers contribute significantly to the overall performance of the TFC membrane. The PSF porous support is widely used in commercial and lab-scale TFC membranes, and its porous structure and other exploitation parameters are set during the non-solvent-induced phase separation (NIPS) process. Since the casting solution properties (e.g., viscosity) and the interactions in a three-component system (polymer, solvent, and non-solvent) play noticeable roles in the NIPS process, polysulfone samples in a wide range of molecular weights (M_w = 76,000–122,000 g·mol⁻¹) with terminal hydroxyl groups were synthesized for the first time. Commercial PSF with predominantly terminal chlorine groups (Ultrason^® S 6010) was used as a reference. The PSF samples were characterized by NMR, DSC, and TGA methods, and the Hansen solubility parameters were calculated. It was found that increasing the ratio of terminal –OH over –Cl groups improved the “solubility” of PSF in N-methyl-2-pyrrolidone (NMP) and water. A direct dependence of the gas permeance of porous supports on the coagulation rate of the casting solution was identified for the first time. It was shown that the use of synthesized PSF (M_w = 76,000 g·mol⁻¹, M_w/M_n = 3.0, (–OH):(–Cl) ratio of 4.7:1) enabled a porous support with a CO₂ permeance of 26,700 GPU to be obtained, while the support formed from a commercial PSF Ultrason^® S 6010 (M_w = 68,000 g·mol⁻¹, M_w/M_n = 1.7, (–OH):(–Cl) ratio of 1:1.9) under the same conditions demonstrated 4300 GPU. The siloxane-based materials were used for the selective layer since the thin films based on rubbery polymers do not undergo the same accelerating physical aging as glassy polymers. Two types of materials were screened for the selective layer: synthesized polymethyltrifluoroethylacrylate siloxane-polydecylmethylsiloxane (50F3) copolymer, and polydimethylsiloxane (PDMS). 50F3 siloxane was studied for gas separation applications for the first time. It was shown that the permeance of composite membranes based on high-performance porous supports from the PSF samples synthesized was 3.5 times higher than that from similar composite membranes based on supports from a commercial Ultrason^® S 6010 PSF with a permeance value of 4300 GPU for CO₂. It was found that the enhanced gas permeance of composite membranes based on the highly permeable porous PSF supports developed was observed for both 50F3 polysiloxane and commercial PDMS. At the same time, the CO₂/CO selectivity of the composite membranes with a 50F3-selective layer (9.1–9.3) is 1.5 times higher than that of composite membranes with a PDMS-selective layer. This makes the F-containing 50F3 polysiloxane a promising polymer for CO₂/CO separation. Full article