Search Results (2,714)

Antimicrobial peptides (AMPs), evolutionarily conserved components of the immune system, have attracted considerable attention as promising therapeutic candidates. Derived from diverse organisms, AMPs represent a heterogeneous class of molecules, typically cationic, which facilitates their initial electrostatic interaction with anionic microbial membranes. Unlike conventional single-target antibiotics, AMPs utilize rapid, multi-target mechanisms, primarily physical membrane disruption, which results in a significantly lower incidence of resistance emergence. Their broad-spectrum antimicrobial activity, capacity to modulate host immunity, and unique mechanisms of action make them inherently less susceptible to resistance compared with traditional antibiotics. Despite these advantages, the clinical translation of natural AMPs remains limited by several challenges, including poor in vivo stability, and potential cytotoxicity. Bioengineering technology offers innovative solutions to these limitations of AMPs. Two techniques have demonstrated promise: (i) a chimeric recombinant of AMPs with stable scaffold, such as human serum albumin and antibody Fc domain and (ii) chemical modification approaches, such as lipidation. This review provides a comprehensive overview of AMPs, highlighting their origins, structures, and mechanisms of antimicrobial activity, followed by recent advances in bioengineering platforms designed to overcome their therapeutic limitations. By integrating natural AMPs with bioengineering and nanotechnologies, AMPs may be developed into next-generation antibiotics. Full article

Water resource management and agricultural practices in the Mediterranean region, characterised by the excessive use of pesticides, pose significant environmental and human health challenges. As they can be easily and inexpensively produced from various biomass sources, biochars are frequently recommended as a low-cost secondary decontamination strategy to address soil contamination problems. This study investigates the properties and sorption behaviours of biochars produced in a low-cost metallic kiln using local rosemary, giant reed, St. John’s wort, olive, cypress, and palm tree biomass residues to evaluate their potential for environmental remediation, with a special focus on the mobility and retention of contaminants. Analytical and experimental techniques were employed to characterise the biochars’ physicochemical attributes and sorptive capacities. The core analyses included measurement of basic physicochemical properties, including pH, electrical conductivity, functional group identification via Fourier transform infrared (FTIR) spectroscopy, and the molarity of ethanol droplet (MED) test to assess the surface hydrophobicity. Batch sorption experiments were conducted using methylene blue (MB) and two fluorescent tracers—uranine (UR) and sulforhodamine-B (SRB)—as proxies for organic contaminants to assess the adsorption efficiency and molecule–biochar interactions. Furthermore, the adsorption isotherms at 20 °C were fitted to different models to assess the biochars’ specific surface areas. Thermodynamic parameters were also evaluated to understand the nature and strength of the adsorption processes. The results highlight the influence of feedstock type on the resulting biochar’s properties, thus significantly affecting the mechanism of adsorption. Rosemary biochar was found to have the highest specific surface area (SSA) and cation exchange capacity (CEC), allowing it to adsorb a wide range of organic molecules. Giant reed and palm tree biochars showed similar properties. In contrast, wood-derived biochars generally showed very low SSA, moderate CEC, and low hydrophobicity. The contrasting properties of the three dyes—MB (cationic), UR (anionic), and SRB (zwitterionic)—enabled us to highlight the distinct interaction mechanisms between each dye and the surface functional groups of the different biochars. The reactivity and sorption efficiency of a biochar depend strongly on both the nature of the target molecule and the intrinsic properties of the biochar, particularly its pH. The findings of this study demonstrate the importance of matching biochar characteristics to specific contaminant types for optimised environmental applications, providing implications for the use of tailored biochars in pollutant mitigation strategies. Full article

Electrocatalytic water splitting offers a promising route to sustainable H₂, but the oxygen evolution reaction (OER) in alkaline media remains the principal bottleneck for activity and durability. This review focuses on alkaline OER and integrates mechanism, kinetics, materials design, and cell-level considerations. Reaction mechanisms are outlined, including the adsorbate evolution mechanism (AEM) and the lattice oxygen mediated mechanism (LOM), together with universal scaling constraints and operando reconstruction of precatalysts into active oxyhydroxides. Strategies for electronic tuning, defect creation, and heterointerface design are linked to measurable kinetics, including iR-corrected overpotential, Tafel slope, charge transfer resistance, and electrochemically active surface area (ECSA). Representative catalyst families are critically evaluated, covering Ir and Ru oxides, Ni-, Fe-, and Co-based compounds, carbon-based materials, and heterostructure systems. Electrolyte engineering is discussed, including control of Fe impurities and cation and anion effects, and gas management at current densities of 100–500 mA·cm⁻² and higher. Finally, we outline challenges and directions that include operando discrimination between mechanisms and possible crossover between AEM and LOM, strategies to relax scaling relations using dual sites and interfacial water control, and constant potential modeling with explicit solvation and electric fields to enable efficient, scalable alkaline electrolyzers. Full article

This report focuses on the oxalate anion radical (C₂O₄^●−) formed during γ-radiolysis of polycrystalline oxalates: protonated oxalic acid (H₂C₂O₄·2H₂O), caesium oxalate (Cs₂C₂O₄), and potassium oxalate monohydrate (K₂C₂O₄·H₂O). Irradiation at 77 K generates stable radical species, revealed by EPR spectroscopy and supported by DFT calculations. In H₂C₂O₄·2H₂O, the primary axial signal (g_avg = 2.0035) is shown to arise from the structural relaxation of the HC₂O₄∙ radical into the intrinsically stable non-planar (D_2d) conformation, resolving the symmetry conflict with the planar crystal precursor. Numerical deconvolution confirmed the co-existence of this radical with the secondary HCO₂^● species, exhibiting distinct relaxation characteristics. In Cs₂C₂O₄, the broad isotropic signal (g ≈ 2.008) is attributed to the D_2d form. Quantitative analysis proved a sharp, thermodynamically driven structural conversion (D_2d→D_2h) upon annealing above 220 K, where the D₂h conformer (g_avg ≈ 2.011) becomes the dominant species (≈73%). In K₂C₂O₄·H₂O, the C₂O₄^●− radical undergoes rapid decomposition into the CO₂^●− radical (g_avg ≈ 2.0007) due to the kinetic instability of the primary species in that matrix. Our findings underscore the crucial role of computational assistance and quantitative numerical fitting in EPR studies: DFT provided crucial assistance and yielded satisfactory agreement in most cases, while clarifying the structural and kinetic stability governed by the local cationic environment. The stability of the most resistant radical forms persists up to 430 K in the caesium salt. Full article

Polyoxometalates (POMs) represent a broad class of anionic inorganic (V, Mo, W) clusters with versatile structures of chemical and physical properties. POMs are inhibitors of many enzymes, including P-type ATPases, well-known to be a target of several approved drugs. Herein, two new hybrid POMs with Mo and mixed V/W, namely (C₂H₈N₁)₆[V₂Mo₁₈O₆₂].3H₂O (1) and (C₄H₁₆N₃)₄[V₂W₄O₁₉]₃.12H₂O (2), were synthesized via wet chemical methods in aqueous solution, and their purity was confirmed and characterized by single X-ray diffraction and infrared spectroscopy. The cations are dimethylammonium ((C₂H₈N)⁺) and diethylenetriammonium ((C₄H₁₆N₃)³⁺), respectively. POMs biological activities were investigated, specifically their inhibitory potential against Ca²⁺-ATPase. The sarcoplasmic reticulum Ca²⁺-ATPase activities were measured spectrophotometrically using the coupled enzyme pyruvate kinase/lactate dehydrogenase assay. For the Ca²⁺-ATPase activity, Dawson (1) showed an IC₅₀ value of 3.4 μM, whereas Lindqvist (2) displayed a value of 45.1 μM. The Ca²⁺-ATPase inhibitory potential of these POMs can be correlated with the net charge (namely 6- and 4-) and the charge density (namely 0.33 and 0.67). A structure–activity-relationship was established for a series of 17 POMs Ca²⁺-ATPase inhibitors correlating IC₅₀ values and POMs net charge and POMs charge density. The described features make Dawson (1) and Lindqvist (2) attractive POMs in a wide range of chemistry fields as well as in biomedical applications. Full article

L-asparaginase (L-ASNase) is a vital enzymatic drug widely used for treating acute lymphoblastic leukemia (ALL) and certain lymphomas. However, its clinical application is often limited by a short plasma half-life, pronounced immunogenicity, and systemic toxicities. To address these challenges, we recently developed conjugates of L-ASNase with cationic polymers, enhancing its cytostatic activity by increasing enzyme binding with cancer cells. The present study focuses on the development of liposomal formulations of E. coli L-asparaginase (EcA) and its conjugates with cationic polymers: the natural oligoamine spermine (spm) and a synthetic polyethylenimine–polyethyleneglycol (PEI-PEG) copolymer. This approach aims to improve enzyme encapsulation efficiency and stability within liposomes. Various formulations—including EcA conjugates with polycations incorporated into 100 nm and 400 nm phosphatidylcholine/cardiolipin (PC/CL, 80/20) anionic liposomes—were synthesized as a delivery system of high enzyme load. Fourier Transform Infrared (FTIR) spectroscopy confirmed successful enzyme association with liposomal carriers by identifying characteristic changes in the vibrational bands corresponding to both protein and lipid components. In vitro release studies demonstrated that encapsulating EcA formulations in liposomes more than doubled their half-release time (T_1/2), depending on the formulation. Cytotoxicity assays against Raji lymphoma cells revealed that liposomal formulations, particularly 100 nm EcA-spm liposomes, exhibited markedly superior anti-proliferative activity, reducing cell viability to 4.5%, compared to 35% for free EcA. Confocal Laser Scanning Microscopy (CLSM) provided clear visual and quantitative evidence that enhanced cellular internalization of the enzyme correlates directly with its cytostatic efficacy. Notably, formulations showing higher intracellular uptake produced greater cytotoxic effects, emphasizing that hydrolysis of asparagine inside cancer cells, rather than extracellularly, is critical for therapeutic success. Among all tested formulations, the EcA-spermine liposomal conjugate demonstrated the highest fluorescence intensity within cells providing enhanced cytotoxicity. These results strongly indicate that encapsulating cationically modified L-ASNase in liposomes is a highly promising strategy to improve targeted cellular delivery and prolonged enzymatic activity. This strategy holds significant potential for developing more effective and safer antileukemic therapies. Full article

Peptide drug development has emerged as a prominent area in pharmaceutical research due to its high specificity and therapeutic potential. However, their biological activity, stability, and bioavailability are significantly influenced by interactions with counter-ions, which electrostatically bind to charged residues on peptide surfaces. This review systematically examines the multifaceted roles of counter-ions in modulating peptide structure and function. Counter-ions are classified into organic/inorganic and anionic/cationic categories, with their selection critically impacting peptide solubility, conformational stability, and activity. Inorganic counter-ions could enhance structural integrity, while organic counter-ions could mitigate toxicity risks. Notably, counter-ions can induce secondary structural transitions, directly affecting biological efficacy. Furthermore, counter-ions play pivotal roles in drug delivery systems, including nanoemulsions, self-emulsifying formulations, and lipid-based nanoparticles, where hydrophobic ion pairing improves encapsulation efficiency and oral bioavailability. In chromatography, ion-pairing reagents optimize peptide separation but may compromise mass spectrometry compatibility. Emerging analytical techniques, such as capillary electrophoresis and liquid chromatography–tandem mass spectrometry (LC-MS/MS), enhance counter-ion detection precision, addressing challenges in pharmaceutical quality control. Despite advancements, gaps remain in understanding ion-specific binding mechanisms and long-term safety profiles. This review underscores the necessity of tailoring counter-ion selection to balance efficacy, stability, and biocompatibility. Future research should prioritize elucidating molecular interaction dynamics and developing safer, high-affinity counter-ions to overcome current limitations in peptide drug development. Full article

In this study, molybdenum disulfide (MoS₂)-based water nanofluids were prepared and stabilized using two surfactants with opposite charges: the cationic cetyltrimethylammonium bromide (CTAB) and the anionic sodium lauryl sulfate (SLS). Different MoS₂:surfactant ratios (1:1, 1:2, and 1:3) were examined to identify the optimal formulation ensuring stable dispersion. Stability was evaluated through dynamic light scattering (DLS), zeta potential, and UV–Vis spectroscopy analyses. The results showed that the MoS₂:SLS (1:3) nanofluid achieved the highest stability, characterized by a zeta potential of −38 mV and a mean particle size of approximately 290 nm. Thermophysical properties were then investigated for nanoparticle concentrations of 0.05, 0.1, and 0.2 wt%. The 0.1 wt% nanofluid exhibited the best performance, showing a thermal conductivity enhancement of about 49% and an increased specific heat capacity compared with pure water. This improvement is attributed to uniform nanoparticle dispersion and enhanced phonon transport. Overall, the results demonstrate that the anionic SLS surfactant at a 1:3 ratio effectively enhances the stability as well as the thermal performance of MoS₂–water nanofluids, making them promising candidates for thermal management and energy systems applications. Full article

Metathesis reactions of Ag[C(CN)₃] with anhydrous YbCl₃ dissolved in water combined with stoichiometric amounts of the alkali-metal salts A[C(CN)₃] (A = Na or K) yield the non-isotypic tetragonal compounds NaYb[C(CN)₃]₄ (P4/nnc with a = 1188.37(9) pm, c = 1232.41(9) pm) and KYb[C(CN)₃]₄ (P4/nbm with a = 1179.26(9) pm, c = 668.73(5) pm). Both crystal structures contain a three-dimensional framework (Niggli formula: $\begin{array}{c}3\\ \infty \end{array}${(Yb[C(CN)₃]_8/2)⁻}) with Yb³⁺ in square antiprismatic coordination of terminal nitrogen atoms (d(Yb–N) = 241–242 pm) from eight planar star-shaped tricyanomethanide anions [C(CN)₃]⁻. The Na⁺ or K⁺ cations occupy vacancies, which provide them with a tetrahedral coordination sphere of nitrogen (d(Na–N) = 239 pm vs. d(K–N) = 276 pm) from four [C(CN)₃]⁻ anions. This difference results from secondary contacts with the central carbon atoms (d(Na–C) = 361 pm vs. d(K–C) = 367 pm) of four different [C(CN)₃]⁻ units, which do not contribute to NaYb[C(CN)₃]₄, but effectuate a lot in the case of KYb[C(CN)₃]₄. The Raman spectrum recorded for NaYb[C(CN)₃]₄ corroborates the presence of a pseudo-D_3h-symmetric tricyanomethanide anion [C(CN)₃]⁻ and the absence of water. Full article

Two single-crystal X-ray structure determinations of 2-aminopyrimidinium hydrogen tri oxofluorophosphate, (C₄H₆N₃)⁺·(HFO₃P)⁻, (I), and bis(2-aminopyrimidinium) trioxofluorophosphate, 2(C₄H₆N₃)⁺·(FO₃P)²⁻, (II), as well as their vibration spectra (FTIR on powder samples and the Raman spectra on unoriented single crystals) with a detailed assignment of vibrational modes are reported. The structure (I) consists of one independent 2-aminopyrimidinium cation and one hydrogen trioxofluorophosphate anion, while (II) consists of two symmetry independent 2-aminopyrimidinium cations and one trioxofluorophosphate anion. In (I), there is an O-H···O hydrogen bond of a moderate strength. A pair of these hydrogen bonds is situated about the symmetry centre and involved in the graph set motif R²₂(8). There are also N-H···O hydrogen bonds of a moderate strength, which are present in both structures while being involved in the graph set motifs R²₂(8), too. In addition, the N-H···O hydrogen bonds form R³₄(10) graph set motifs in (II). The latter motifs form ribbons which propagate parallel to the unit-cell axis a. In both structures, there are present π···π-electron ring interactions into which the primary amine groups are involved. In both structures, there are also present weak C-H···N hydrogen bonds with participation of the non-protonated ring N-atoms. The fluorine participates in the C-H···F hydrogen bonds in both title structures. The P-F distances are normal in both anions. The structure (I) differs from the known structure of 2-aminopyrimidinium hydrogen phosphite, the compositional isomer, though the main hydrogen bonds show similar geometry in both structures. The crystal of (I) was twinned. Full article

Although fast-paced ongoing industrial growth, on the one hand, enhances the lifestyle of the population, on the other hand, it affects human health and the environment as a result of the discharge of pollutants. To address this, designing a novel and effective photocatalyst is necessary to mitigate increasing environmental pollutants. In the present work, we aim to synthesize a single-phase high-entropy zirconate pyrochlore oxide (Ce_0.2Pr_0.2Zn_0.2Nd_0.2Tb_0.2)₂Zr₂O₇ using a modified Pechini method. The physicochemical properties of the prepared nanoparticles were investigated using X-ray diffraction, UV-visible spectroscopy, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The photocatalytic properties were examined using cationic dye (methylene blue), anionic dye (Congo red), and Cr(VI). Photocatalytic degradation experiments demonstrate exceptional efficiency in the removal of persistent organic pollutants. The photocatalytic results indicate that the prepared high-entropy (Ce_0.2Pr_0.2Zn_0.2Nd_0.2Tb_0.2)₂Zr₂O₇ zirconate pyrochlore oxide could effectively degrade dyes and reduce Cr(VI). Radical trapping experiments indicate that the degradation of dyes was driven by the hydroxyl radicals, superoxide radicals, and holes. Furthermore, the position of the valence band and conduction band promoted efficient photocatalytic reaction kinetics. The prepared photocatalyst remains structurally stable and can be reused three times without losing activity. Full article

This paper presents comprehensive studies of pitting corrosion, which precedes the appearance of fistulas in galvanized steel pipelines of hot and cold water supply systems. Corroded galvanized pipes taken out from water supply systems within their operation and scale samples were the subject of this research. The current work continues the research on one of the four structural elements of tubercles—the dense layer. The corrosion of the zinc coating and the steel base of pipes inside the tubercles led to a gradual increase in the concentration of a solution containing components of the corroding metal (zinc and iron cations) and anions in water (mainly chlorides and sulfates). To explain the corrosion under the tubercles, their dense layer was compared with an anion exchange membrane with selective properties, which provided the primary concentration of the salt solution in the structure of the tubercles with a significant increase in the concentration of aggressive anions compared to the source water. The formation of fistulas in the cavity leads to a secondary concentration of solution inside the tubercle, mainly consisting of iron chloride. At the same time, due to the hydrolysis of the formed iron salts and a decrease in pH, the corrosion rate increases and becomes independent of external conditions. This article summarizes ten years of experience in examining corrosion of steel pipes from external and internal water supply systems. Full article

Understanding the interactions between ionic liquid ions and lithium-metal surfaces is critical for designing safer and more efficient lithium metal batteries. In this work, we use density functional theory to investigate the electronic structure, binding energies, work-function shifts and interfacial charge redistribution of several ionic liquid ions, including FSI⁻, TFSI⁻, ${\mathrm{P}\mathrm{F}}_6^{-}$, ${\mathrm{B}\mathrm{F}}_4^{-}$, DFOB⁻, Pyr14⁺, and EMIM⁺, on a Li-metal anode (Li_m). Absorption orientation-dependent effects are examined for each molecule. Specifically, differences in charge density and electron localization function analyses revealed unique patterns of electron accumulation and delocalization that highlighted specific atomic roles in interfacial bonding. Interfacial charge transfer is analyzed through Bader charges, revealing a moderate charge redistribution for the cations (EMIM⁺, Pyr14⁺), and a more significant charge uptake for the reactive anions (FSI⁻, TFSI⁻, DFOB⁻). Among cations, EMIM⁺ was determined to have the most interfacial stability, while Pyr14⁺ displayed mid-level reactivity. For the anions, varying tendencies for bond formation with lithium metal and potential fragmentation could be determined. Overall, these discoveries detail an atomistic analysis of ionic liquid to Li_m interactions providing additional pathways for molecular design techniques to stabilize electrolytes performing not high-cost computational calculations. Full article

Active compounds used in agriculture are mainly in the form of acids. This applies primarily to substances that are inducers of systemic acquired resistance, which is one of the most promising methods of supporting plants in the fight against pathogens. The physicochemical properties and biological activity of such substances can be improved by derivatizing them to salt forms. We used the concept of ionic liquids to obtain novel compounds in the form of chlormequat ionic liquids. In this study we present synthesis and characterization of a series of novel ionic liquids composed of the chlormequat cation paired with plant resistance-inducing anions, including salicylic acid and its chlorinated derivatives, nicotinic acid and isonicotinic acid. The results indicate that the new compounds in the form of salts are characterized by better biological activity related to SAR induction and lower phytotoxicity compared to the parent compounds as their equivalents in acid forms. The obtained compounds demonstrated the ability to activate defense responses in tobacco and to reduce susceptibility to viral infection, highlighting their potential for further application in crop protection. Full article

Synthesis of anionic metal–organic framework Na[Ce(BDC)₂(DMF)₂] based on cerium (III)–sodium terephthalate was performed. The crystal structure, studied by the Rietveld method, consists of anionic [Ce(BDC)₂]⁻ layers, connected by interlayer sodium cations in a 3D network. Variable-temperature PXRD, total X-ray scattering with pair distribution function analysis, and DFT calculations revealed framework structure stability upon DMF elimination and thermal treatment up to 300 °C. Modification with copper cations was performed using wetness impregnation with a Cu(NO₃)₂ methanol solution to obtain a catalyst for carbon monoxide oxidation. Cu²⁺@Na[Ce(BDC)₂(DMF)₂] in situ decomposition leads to the catalytic activity of the resulting CuO/CeO₂ composite during CO gas oxidation by air. Full article