Search Results (107)

Conventional dental materials with organised crystal structures exhibit limitations in corrosion resistance, bioactivity, and drug delivery capability. In contrast, amorphous nanomaterials offer potential advantages in overcoming these limitations due to their unique structural properties. They are characterised by a non-crystalline, disordered atomic structure and are similar to a solidified liquid at the nanoscale. Among the amorphous nanomaterials used in dentistry, there are five major categories: calcium-, silicon-, magnesium-, zirconia-, and polymer-based systems. This study reviewed these amorphous nanomaterials by investigating their synthesis, properties, applications, limitations, and future directions in dentistry. These amorphous nanomaterials are synthesised primarily through low-temperature methods, including sol–gel processes, rapid precipitation, and electrochemical etching, which prevent atomic arrangements into crystalline structures. The resulting disordered atomic configuration confers exceptional properties, including enhanced solubility, superior drug-loading capacity, high surface reactivity, and controlled biodegradability. These characteristics enable diverse dental applications. Calcium-based amorphous nanomaterials, particularly amorphous calcium phosphate, demonstrate the ability to remineralise tooth enamel. Silicon-based amorphous nanomaterials function as carriers that can release antibacterial agents in response to stimuli. Magnesium-based amorphous nanomaterials are antibacterial and support natural bone regeneration. Zirconia-based amorphous nanomaterials strengthen the mechanical properties of restorative materials. Polymer-based amorphous nanomaterials enable controlled release of medications over extended periods. Despite the advances in these amorphous nanomaterials, there are limitations regarding material stability over time, precise control of degradation rates in the oral environment, and the development of reliable large-scale manufacturing processes. Researchers are creating smart materials that respond to specific oral conditions and developing hybrid systems that combine the strengths of different nanomaterials. In summary, amorphous nanomaterials hold great promise for advancing dental treatments through their unique properties and versatile applications. Clinically, these materials could improve the durability, bioactivity, and targeted drug delivery in dental restorations and therapies, leading to better patient outcomes. Full article

Microwave-Induced Hydrogen Plasma (MIHP) is introduced as a novel synthesis route for producing high-entropy carbides (HECs), offering an alternative to conventional mechanical alloying and/or sintering techniques. In this study, a representative HEC composition, ${\mathrm{MoNbTaVWC}}_5$, was successfully synthesized using MIHP processing at 200 Torr. The process employs microwave energy to generate hydrogen plasma to facilitate carbothermal reduction of metal oxide precursors. The plasma environment generates abundant reactive atomic hydrogen species, which enhance reaction spontaneity and promote efficient HEC formation. X-ray diffraction confirmed the formation of a single-phase rocksalt-type face-centered cubic structure. Scanning electron microscopy combined with energy-dispersive X-ray spectroscopy confirmed uniform elemental distribution within the synthesized microstructure. Nanoindentation measurements yielded hardness and elastic modulus values consistent with literature reports for similar compositions. X-ray photoelectron spectroscopy confirmed the chemical state of carbon to be primarily bonded with metals as carbides, with only minor oxygen present as metal-oxides. Raman spectroscopy performed over the 750–1900 ${\mathrm{cm}}^{-1}$ range yielded a featureless spectrum with no detectable D or G bands often observed for sp²-hybridized disordered carbon, graphite, or graphene materials. These results validate the structural and chemical purity of the synthesized HECs. This work aims to demonstrate the feasibility and reproducibility of MIHP as a synthesis method for HECs. Full article

Proteins play an important role in living organisms, and, for most of them, the function depends on their structure. There are some proteins that have similar properties but different structures. An example of this is ice-binding proteins (IBPs), which have different structures but share the ability to bind to ice. Many organisms have evolved such proteins to help them survive in cold environments. Therefore, it is important to study the oligomeric state of the active form in solutions. The activity of IBP is related to the area of their ice-binding site. We have demonstrated the presence of oligomeric forms of protein in solution using multiple techniques, such as mass spectrometry, native gel electrophoresis, atomic force microscopy (AFM), isothermal titration calorimetry (ITC) and small-angle X-ray scattering (SAXS). It is noteworthy that, to date, there have been no reports of the oligomerization of ice-binding protein from Longhorn sculpin. Additionally, our findings suggest that larger molecules may influence the ability of proteins to bind to ice. In our study, the ice-binding protein forms elongated assemblies with limited intermonomer interfaces. The combination of SAXS and AFM data indicates a structure that combines compactness and flexibility and probably consists of four monomeric units. The employment of molecular modelling methodologies resulted in the attainment of a tetrameric complex that is in alignment with AFM data. Details of oligomers observed using the methods in our study emphasize the importance of different techniques that complement each other in resolving structural features. Additionally, we suggest that the protein particles, which were dispersed on the surface, exhibit softness or the form planar complexes with loose quaternary structures. It is conceivable that, depending on ionic strength and/or temperature, the various oligomeric forms of the ice-binding protein form thermodynamically more favorable complexes than their monomeric forms. Full article

Soil contamination with heavy metals is a persistent challenge in the arid regions of Kazakhstan. This study evaluates the phytoremediation potential of sweet sorghum (Sorghum bicolor L.), a drought-tolerant crop with a well-developed root system, using a combination of in vitro and analytical approaches. In vitro culture of somatic cells revealed clear genotype-dependent differences in callus induction and morphogenesis, with Hybrid-2 and SAB-3 exhibiting the highest regenerative capacity and thus the greatest suitability for further biotechnological improvement and stress-tolerance selection. Analysis of metal distribution, based on atomic absorption spectroscopy (AAS), demonstrated that S. bicolor predominantly retained Pb, Cd, and Co in the root system. Cobalt accumulated to 12.7 ± 1.32 mg/kg under 1 MAC and 16.87 ± 2.78 mg/kg under 2 MAC, accounting for more than half of the metal absorbed by plants. Cadmium showed a similar root-dominant pattern, whereas lead exhibited the lowest mobility and remained almost entirely sequestered in roots, with translocation factors consistently below unity (TF < 1). Overall, these findings confirm the suitability of sweet sorghum as an environmentally sustainable species for the phytostabilization of Pb-, Cd-, and Co-contaminated soils in arid environments and highlight the value of genotype pre-selection under stress conditions for optimizing phytoremediation performance. Full article

Photosystem I (PSI) is a photosynthetic protein–pigment complex that, upon photoexcitation, transfers electrons to ferredoxin, facilitating the production of NADPH. Isolated PSI reaction centers (RCs) have also been used in hybrid systems to reduce protons and produce ‘biohydrogen’. This review article examines how various cyanobacteria with similar photosynthetic machinery utilize different wavelengths of light to execute photosynthetic electron transport through PSI. Key factors, such as, the structure of the electron transfer cofactors, the protein environment surrounding the primary donor pigments and hydrogen-bonding interactions with the surrounding protein matrix are analyzed to understand their roles in maintaining efficient electron transfer when it is driven using photons of different energies. We compare PSI complexes with known atomic structures from four species of cyanobacteria, Thermosynechococcus elongatus, Acaryochloris marina, Halomicronema hongdechloris, and Fischerella thermalis. T. elongatus is typical of most oxygenic photosynthetic organisms in that it requires visible light and uses only chlorophyll a (Chl a) in PSI. In contrast, H. hongdechloris and F. thermalis are photoacclimating species capable of producing Chl f and Chl d that use red light when little visible light is available. A. marina, on the other hand, is adapted to red light conditions and consistently utilizes Chl d as its primary photosynthetic pigment, maintaining a stable pigment composition. Here, we explore the structural and functional differences between the PSI RCs of these organisms and the impact of these differences on electron transport. The structural differences in the cofactors influence both the absorption wavelengths of the cofactors and the energy levels of the intermediate states of electron transfer. An analysis of the surrounding protein shows how it has been adapted and underscores the interplay between the pigment structure, protein environment, and hydrogen bonding networks in tuning the efficiency and adaptability of photosynthetic mechanisms across different species of cyanobacteria. Full article

(1) Background: The extracellular matrix (ECM) is a natural scaffold for cells, creating a three-dimensional architecture composed of fibrous proteins (mainly collagen) and proteoglycans, which are synthesized by resident cells. In this study, a physiological hypoxic environment was utilized to enhance ECM production by human mesenchymal stem cells (hMSCs), a process relevant to tissue engineering and regenerative medicine. (2) Methods: hMSCs were treated with deferoxamine (DFO), a pharmaceutical hypoxia-mimetic agent that induces cellular responses similar to low-oxygen conditions through stabilization of hypoxia inducible factor-1α (HIF-1α). The time points 0 h 24 h, 3 h 24 h, and 24 h 24 h refer to DFO being added immediately after cell seeding (before cells adhesion), 3 h after cell seeding (during initial cells attachment), and 24 h after cell seeding (after focal adhesions formation and actin organization), respectively, to evaluate the influence of cell adhesion on ECM deposition. hMSCs incubated in culture media were subsequently exposed to DFO for 24 h. Samples were then subjected to cell viability tests, scanning electron microscopy (SEM), atomic force microscopy (AFM) and laser scanning confocal microscopy (CLSM) assessments. (3) Results: Viability tests indicated that DFO concentrations in the range of 0–300 µM were non-toxic over 24 h. The presence of collagen fibers in the DFO-derived ECM was confirmed with anti-collagen antibodies under CLSM. Increased ECM secretion was observed under the following conditions: 3 μM DFO (24 h 24 h), 100 μM DFO (0 h 24 h) and 300 μM DFO (3 h 24 h). SEM and AFM images revealed the morphology of various stages of collagen formation with both collagen fibrils and fibers identified. (4) Conclusions: Our preliminary study demonstrated enhanced ECM secretion by hMSC treated with DFO at concentrations of 3, 100, and 300 µM within a short cultivation period of 24–48 h without significant affecting cell viability. By mimicking physiological processes, it may be possible to stimulate endogenous tissue regeneration, for example, at an injury site. Full article

The ability of earth-abundant metals to serve as catalysts for the oxygen reduction reaction is of increasing importance given the prominence of this reaction in several emerging technologies. It is now recognized that both the primary and secondary coordination environments of these catalysts can be modulated to optimize their performance. In this present work, we describe two Co^II complexes [Co^II(PaPy₂Q)](OTf) (1) and [Co^II(PaPy₂N)](OTf) (2) that catalyze chemical and electrochemical dioxygen reduction. Both 1 and 2 contain Co^II centers in a N₅⁻ coordination environment, but 2 has a naphthyridine group that places a nitrogen atom in the secondary coordination sphere. Solid-state X-ray crystallography and solution-state spectroscopic measurements reveal that, apart from this second-sphere nitrogen in 2, complexes 1 and 2 have essentially identical properties. Despite these similarities, 2 performs the chemical reduction of dioxygen ~10-fold more rapidly than 1. In addition, 2 has an enhanced performance in the electrochemical reduction of dioxygen compared to 1. Both complexes yield a significant amount of H₂O₂ in the chemical reduction of dioxygen (>25%). The enhanced catalytic performance of 2 is attributed to the presence of the second-sphere nitrogen atom, which might enable the efficient protonation of cobalt–oxygen intermediates formed during turnover. Full article

The study of the impact of anthropogenic and natural pollution on living organisms has become a major social issue. In this context, the objective of this work is to assess the use of the polychaete annelid Hediste diversicolor as a bioindicator organism for the quality of the marine environment. The concentration of four heavy metals (lead, copper, zinc, and cadmium) was determined in natural populations of H. diversicolor captured from four locations along the Tunisian coast using atomic absorption spectroscopy. Concentration ranges (µg/g dry weight) across all sites were as follows: Cd (0.12–0.43), Cu (3.80–6.45), Zn (18.35–42.78), and Pb (22.64–63.91). Statistical analysis confirmed significant spatial variation (Pb: F = 12.15, p < 0.001; Zn: F = 3.32, p = 0.04; Cd: F = 48.66, p < 0.001; Cu: F = 9.08, p < 0.001), with peak Pb in Bizerte and Cu in Sfax. These results highlight the influence of local environmental factors, such as industrial and urban pollution on metal accumulation in Hediste diversicolor. In this study, the accumulation of the analyzed elements in the tissues of H. diversicolor follows an increasing order as follows: Cd < Cu < Zn < Pb. Additionally, lead metal concentrations were higher than those of cadmium, zinc, and copper for all four studied locations. To our knowledge, this is the first study in Tunisia to assess heavy metal accumulation in H. diversicolor. The recorded levels were similar to, or lower than, those reported in other studies worldwide. These findings underscore the potential of H. diversicolor as a sensitive and effective bioindicator for monitoring coastal contamination and guiding environmental management strategies in Tunisia. Full article

Clay minerals contain significant amounts of Fe in their alumosilicate framework, and this structural Fe can be reduced and re-oxidized, constituting a potentially renewable source of reduction equivalents in sedimentary environments. However, dissolution and/or clay mineral transformations during microbial Fe reduction contradict this concept. Here, we investigate how Fe reduction and re-oxidation affect the propensity of Fe to be released from the clay mineral structure and use selective sequential extractions in combination with Mössbauer spectroscopy. Negligible amounts of Fe were released in the sequential extraction of high Fe content clay minerals NAu-1 and NAu-2. Once aqueous Fe(II) was added as a reductant, the extraction procedure recovered the initially added Fe amount and up to 30% of the Fe from the clay mineral structure as both Fe(II) and Fe(III). Similar extents of Fe mobilization were found for clay minerals partly reduced (7%–20%) with dithionite, suggesting that mobilization was reduction-induced and independent of the source of reduction equivalents (Fe(II), dithionite). Although higher Fe reduction extents mobilized more structural Fe, i.e., >90% in fully reduced clay minerals, re-oxidation largely reverted the reduction-induced Fe mobilization in clay minerals. Our finding of reduction-driven Fe mobilization provides a plausible explanation for conflicting reports on Fe release from clay minerals and how extensive Fe atom exchange between aqueous and clay mineral Fe occurs. Full article

Coumarin and cytisine and their derivatives have significant biological activity. In addition, the electronic properties of coumarin derivatives are very sensitive to the molecular environment, which allows for their use as sensors for bioluminescent imaging. Due to the fact that cytisine exhibits high activity in binding to nicotinic acetylcholine receptors, a compound combining parts of cytisine and coumarin may have a broader spectrum of biological activity and also act as a photoactive element for promising use in optoelectronic devices. This article reports the synthesis of a crystalline cytisine–coumarin complex (IUPAC: N-(2-oxo-2H-chromene-3-carbonyl)cytisine), along with the results of both theoretical and experimental investigations of its structural and electronic properties. The structure of this new compound was established on the basis of X-ray diffraction and Fourier transform infrared spectroscopy data and was confirmed through density functional theory calculations using periodic crystal and single-molecule approaches. Interpretations of the IR absorption peaks and the atomic patterns of the vibrational modes are given. The electronic band structure and the contributions of individual atoms to the electronic density of states are analyzed. The structural and optical properties considered may be useful for quality control of the compound and for studying similar matrices. Full article

Hydroperoxyalkylperoxy radicals (•OOQOOH) are important intermediates in the low-temperature oxidation chemistry of conventional fuels. In these species, a hydrogen atom may migrate from a non-adjacent carbon to the peroxy group, forming a dihydroperoxyalkyl radical (•P(OOH)₂). This research delves into the theoretical kinetics of a set of 110 H-migration reactions in normal-alkyl cyclohexanes, calculating high-pressure limit rate constants for these reactions. The reactions are further classified into 15 subclasses based on distinctions in the reaction center and its environment, with rate rules derived by averaging the rate constants within each subclass. A comparison of our calculated rate constants for specific H-migration reactions of •OOQOOH with existing mechanisms and similar reactions in non-cyclic alkanes reveals significant disparities, emphasizing the necessity for precise rate constants tailored to normal-alkyl cyclohexanes. Ethyl cyclohexane mechanisms and n-propyl cyclohexane mechanisms sourced from studies have been improved with high-pressure limit rate constants from this study. Simulations of the low-temperature combustion of ethyl cyclohexane and n-propyl cyclohexane show that the predictions from the updated mechanisms align more closely with the experimental data under specific conditions compared to the original mechanism. Full article

Ion interactions with molecular structures give insights into physicochemical processes in the cosmos, radiation damage, plasma, combustion, and biomass conversion reactions. At the atomic scale, these interactions lead to excitation, ionization, and dissociation of the molecular components of structures found across all these environments. Furan, cyclic aromatic ether (C₄H₄O), serves as a gas-phase deoxyribose analog and is crucial for understanding key pathways in renewable biomass conversion, as its derivatives are versatile molecules from lignocellulosic biomass degradation. Therefore, collisions of H₃⁺ and C⁺ ions with gas-phase furan molecules were investigated in the 50–1000 eV energy range, exploiting collision-induced emission spectroscopy. High-resolution fragmentation spectra measured at 1000 eV for both cations reveal similar structures, with C⁺ collisions resulting in more significant furan fragmentation. Relative cross-sections for product formation were measured for H₃⁺ + C₄H₄O collisions. Possible collisional processes and fragmentation pathways in furan are discussed. These results are compared with those for tetrahydrofuran and pyridine to illustrate how the type and charge of the projectile influence neutral fragmentation in heterocyclic molecules. Full article

Additives are compounds used for material to increase specific properties. When used for polymers, they extend their life and contribute to environmental sustainability. This article presents the study findings related to 24 additives—antioxidants, UV stabilizers, and quenchers—using cheminformatics methods. The compounds’ characteristics (e.g., number of atoms, functional groups) were emphasized, followed by some descriptors. The Tanimoto coefficient, computed based on the maximum common structure algorithm, and the overlap coefficient indicated the degree of similarity between the molecules. The molecules were grouped by binning and hierarchical clustering (HC) based on the extracted results. In the last case, two scenarios were considered—with four (CL1–CL4) and six clusters (CL1.1, CL1.2, CL2, CL3, CL4.1, CL4.2) being built. Considering the mechanical properties of the compounds and the standard deviation and amplitude of their values, the most homogenous class was CL2 (respectively CL4.2). Considering the toxicity of additives, the highest possible negative impact on the environment is that of the compounds in CL1 and CL3. The clustering results guide the selection of additives with reduced environmental impact, thereby supporting the development of sustainable polymer formulations aligned with circular economy principles. Full article

Zoharite (IMA 2017-049), (Ba,K)₆ (Fe,Cu,Ni)₂₅S₂₇, and gmalimite (IMA 2019-007), ideally K₆□Fe²⁺₂₄S₂₇, are two new sulfides of the djerfisherite group. They were discovered in an unusual gehlenite–wollastonite paralava with pyrrhotite nodules located in the Hatrurim pyrometamorphic complex, Negev Desert, Israel. Zoharite and gmalimite build grained aggregates confined to the peripheric parts of pyrrhotite nodules, where they associate with pentlandite, chalcopyrite, chalcocite, digenite, covellite, millerite, heazlewoodite, pyrite and rudashevskyite. The occurrence and associated minerals indicate that zoharite and gmalimite were formed at temperatures below 800 °C, when sulfides formed on external zones of the nodules have been reacting with residual silicate melt (paralava) locally enriched in Ba and K. Macroscopically, both minerals are bronze in color and have a dark-gray streak and metallic luster. They are brittle and have a conchoidal fracture. In reflected light, both minerals are optically isotropic and exhibit gray color with an olive tinge. The reflectance values for zoharite and gmalimite, respectively, at the standard COM wavelengths are: 22.2% and 21.5% at 470 nm, 25.1% and 24.6% at 546 nm, 26.3% and 25.9% at 589 nm, as well as 27.7% and 26.3% at 650 nm. The average hardness for zoharite and for gmalimite is approximately 3.5 of the Mohs hardness. Both minerals are isostructural with owensite, (Ba,Pb)₆(Cu,Fe,Ni)₂₅S₂₇. They crystallize in cubic space group Pm$\overline{3}$m with the unit-cell parameters a = 10.3137(1) Å for zoharite and a = 10.3486(1) Å for gmalimite. The calculated densities are 4.49 g·cm⁻³ for the zoharite and 3.79 g·cm⁻³ for the gmalimite. The primary structural units of these minerals are M₈S₁₄ clusters, composed of MS₄ tetrahedra surrounding a central MS₆ octahedron. The M site is occupied by transition metals such as Fe, Cu, and Ni. These clusters are further connected via the edges of the MS₄ tetrahedra, forming a close-packed cubic framework. The channels within this framework are filled by anion-centered polyhedra: SBa₉ in zoharite and SK₉ in gmalimite, respectively. In the M₈S₁₄ clusters, the M atoms are positioned so closely that their d orbitals can overlap, allowing the formation of metal–metal bonds. As a result, the transition metals in these clusters often adopt electron configurations that reflect additional electron density from their local bonding environment, similar to what is observed in pentlandite. Due to the presence of shared electrons in these metal–metal bonds, assigning fixed oxidation states—such as Fe²⁺/Fe³⁺ or Cu⁺/Cu²⁺—becomes challenging. Moreover, modeling the distribution of mixed-valence cations (Fe²⁺/³⁺, Cu⁺/²⁺, and Ni²⁺) across the two distinct M sites—one located in the MS₆ octahedron and the other in the MS₄ tetrahedra—often results in ambiguous outcomes. Consequently, it is difficult to define an idealized end-member formula for these minerals. Full article

Bio-oil energy use in agricultural systems provides sustainable solutions for powering machinery operations and heating and cooling environments in facilities. However, its potential in South Africa is constrained by the limited availability of energy substrate that does not compromise food production, land use, and water resources. This study investigated the physical and chemical properties of six invasive alien plant species (IAPs), three woody species (Acacia mearnsii, Eucalyptus grandis, and Pinus patula), and three nonwoody species (Lantana camara, Chromolaena odorata, and Solanum mauritianum) to assess their suitability for bio-oil production. Key analyses included structural, elemental, proximate, atomic ratio, higher heating value (HHV), and thermogravimetric analysis (TGA) analyses. The results showed that woody IAPs had a significantly higher structural composition (p < 0.05), improving bio-oil yield. The bio-oil can be blended with diesel for agricultural use, while lignin-derived biochar serves as a soil amendment. Higher carbon and hydrogen contents enhanced HHV and combustion, while lower nitrogen and sulfur levels reduced emissions. Despite oxygen hindering pyrolysis, its bioactive properties support crop protection. Compared to South African coal, IAP-derived bio-oil shares similarities with peat coal and could be used for greenhouse heating. This study promotes energy efficiency in agriculture, reduces fossil fuel dependence, and supports environmental sustainability by repurposing IAPs. Additional studies should focus on lignin pretreatment and bio-oil upgrading to reduce oxygenated compounds. Full article