Search Results (162)

Background: Magnesium sulfate (MgSO₄) has been investigated as an adjuvant in perioperative analgesia because of its antagonistic effects on the N-methyl-D-aspartate receptor (NMDA receptor) and its potential to attenuate central sensitization. However, clinical findings regarding its analgesic efficacy remain inconsistent across surgical procedures. Lumbar microdiscectomy is a common spinal procedure in which effective early postoperative pain control is important for patient comfort and early mobilization. This study aimed to evaluate the effect of intraoperative MgSO₄ administration on early postoperative analgesia and perioperative outcomes in patients undergoing lumbar microdiscectomy. Methods: This retrospective single-center cohort study included thirty-eight patients with American Society of Anesthesiologists (ASA) physical status I–II who underwent elective single-level lumbar microdiscectomy under general anesthesia. Patients were divided into two groups according to intraoperative magnesium administration: a control group receiving standard anesthesia without MgSO₄ (n = 19) and an MgSO₄ group receiving an intravenous MgSO₄ bolus of 30 mg/kg followed by a continuous infusion of 10 mg/kg/h until skin closure (n = 19). Postoperative pain intensity was assessed using the Numeric Rating Scale (NRS) at 0, 5, 10, 15, and 30 min after admission to the post-anesthesia care unit. Secondary outcomes included intraoperative remifentanil consumption, extubation time, and time to first mobilization. Complementary in silico analyses included molecular docking and protein–protein interaction (PPI) network analysis. Results: Postoperative NRS scores were numerically lower in the MgSO₄ group; however, between-group differences were not statistically significant. Mean intraoperative remifentanil consumption was numerically lower in the MgSO₄ group (236 ± 166 µg) compared with the control group (319 ± 298 µg), without statistical significance (p = 0.27). Repeated-measures analysis demonstrated the significant effect of time on postoperative NRS scores, whereas the overall group effect was not significant. Molecular analyses indicated stable morphine binding to opioid receptors and highlighted glutamatergic signaling components as central nodes within the interaction network. Conclusions: Intraoperative MgSO₄ administration was not associated with significant improvements in early postoperative pain scores or perioperative recovery parameters following lumbar microdiscectomy. Molecular analyses provide exploratory in silico insights and should be interpreted cautiously given the retrospective design and the in silico nature of these findings. Full article

In this work, we designed non-viral gene delivery vector systems based on three poly(2-ethyl-2-oxazoline)-ran-poly[2-(3-butenyl)-2-oxazoline] copolymers functionalized by primary, secondary, and tertiary amino groups. The impact of copolymer structure and composition was sought through the examination of basic physicochemical and biological parameters. The complexation ability of copolymers with plasmid DNA was studied by ethidium bromide quenching assay. The polyplex particles size and ζ-potential were determined by dynamic and electrophoretic light scattering. The release ability of copolymers was assessed by competitive displacement of DNA using dextran sulfate. The biological performance of amino-functionalized poly(2-ethyl-2-oxazoline)-ran-poly[2-(3-butenyl)-2-oxazoline] based gene delivery systems was evaluated, and their behavior under various environmental conditions, such as pH and ionic strength, was investigated. Cytotoxicity was assessed in two human lung-derived cell lines, and the ability of the copolymers to mediate plasmid DNA delivery and expression was examined. The resulting polyplex nanoparticles exhibited the ability to release DNA molecules and sensitivity to alterations in pH and ionic strength. All systems showed high biocompatibility and were able to mediate plasmid DNA delivery, resulting in detectable EGFP expression in vitro. The vector properties were found to be driven by a multifactorial interplay among hydrophobic character, thermoresponsive behavior, polymer mobility, charge accessibility, intracellular environmental responsiveness, secondary structure effects, etc. The copolymer bearing primary amino groups displayed a distinct balance between DNA binding and release, characterized by moderate complex stability and enhanced sensitivity to environmental changes. These findings provide mechanistic insight into how amino functionality and polymer structure influence the structure–property–behavior relationships of polyoxazoline-based non-viral gene delivery systems. Full article

Colistin sulfate (COL), a critical last-line antibiotic, poses a severe environmental threat due to its persistence and role in spreading mobile resistance genes. This study introduces a novel quaternary Ni-Co-Zn-Al layered double-hydroxide/activated carbon composite (Q-LDH/AC) for highly efficient COL remediation. The composite’s unique architecture, revealed through comprehensive characterization, enables an exceptional adsorption capacity of 952.52 mg·g⁻¹ under optimal conditions (pH 7, 55 °C), a value that significantly surpasses those reported for most previous adsorbents. The process was spontaneous and endothermic, with kinetics and isotherms best described by the pseudo-second-order and Langmuir–Freundlich models, respectively, indicating a complex mechanism dominated by chemisorption on both homogeneous and heterogeneous sites. A key innovative feature is the successful regeneration and reusability of the composite, which retained over 70% efficiency after five cycles, enhancing its potential for practical, cost-effective water treatment applications. The thermodynamic parameters (ΔG° = −8140.68 kJ/mol, ΔH° = +61.22 kJ/mol) indicate that the reaction is spontaneous and endothermic. The interaction mechanism of COL on Q-LDH/AC can be deduced by FT-IR including hydrogen bonding, π-π bonding, electrostatic interactions, and surface complexation. Beyond mere regeneration, this work demonstrates a pioneering circular economy strategy by repurposing the spent COL-laden adsorbent not as waste, but as a high-performance electrocatalyst. In direct urea fuel cell tests, this electrode achieved a superior and stable current density of 45.63 mA/cm² for Q-LDL/AC, substantially outperforming the pristine Q-LDH/AC/COL (206.63 mA/cm²) and highlighting how the captured pollutant enhances functionality. This dual-purpose approach successfully closes the loop, transforming the environmental liability of antibiotic-laden waste into a valuable resource for energy applications. With a production cost of 2.755 USD/g, this work presents not only a highly effective adsorbent but also a transformative, circular strategy that simultaneously addresses water pollution and energy recovery. These findings offer a promising dual-purpose solution for mitigating the environmental spread of antibiotic resistance through a sustainable cycle that enables efficient antibiotic removal from wastewater while simultaneously converting the captured pollutant into a useful energy resource. Full article

Phosphogypsum (PG), a calcium sulfate-rich byproduct of phosphate fertilizer production, is generated in vast quantities worldwide and represents a major environmental management challenge. At the same time, its chemical composition makes PG a potentially valuable soil amendment, particularly for the reclamation of saline, sodic, and acidic soils. This review critically synthesizes current knowledge on PG generation processes, physicochemical properties, agronomic performance, and associated environmental and health risks. Evidence from peer-reviewed studies demonstrates that appropriately managed PG applications can improve soil structure, enhance water infiltration, reduce sodium toxicity, alleviate aluminum stress, and increase crop productivity. However, PG contains variable levels of impurities, including heavy metals and naturally occurring radionuclides, which raise concerns regarding soil contamination, groundwater pollution, food safety, and human health, especially under high or repeated application rates. Regulatory frameworks governing PG use differ substantially between regions, reflecting inconsistencies in waste classification, radiological thresholds, and leaching criteria. This review highlights key knowledge gaps related to contaminant mobility, bioavailability, and long-term ecological impacts and discusses mitigation strategies such as purification, controlled application rates, and integrated regulatory oversight. By balancing agronomic benefits against environmental risks, this work provides a comprehensive framework for the safe valorization of phosphogypsum in agriculture, supporting sustainable land management and circular economy objectives. Full article

Tropical cyclones can rapidly alter watershed chemistry by shifting hydrologic pathways and mobilizing stored nutrients, yet these disturbances often remain undetected when storms cause little visible flooding or geomorphic damage. During Hurricane Helene 2024, intense rainfall across the Oconee River watershed in Georgia generated sharp increases in discharge that triggered substantial nutrient export despite minimal physical alteration to the landscape. High-frequency measurements of nitrate, phosphate, and sulfate in urban, forested, and recreational settings revealed pronounced and synchronous post-storm increases in all three solutes. Nitrate showed the strongest and most persistent response, with mean concentrations increasing from approximately 1–3 mg/L during pre-storm conditions to 6–14 mg/L post-storm across sites, and remaining elevated for several months after hydrologic conditions returned to baseline. Phosphate concentrations increased sharply during the post-storm period, rising from pre-storm means of ≤0.3 mg/L to a post-storm average of 1.5 mg/L, but declined more rapidly during recovery, consistent with sediment-associated mobilization and subsequent attenuation. Sulfate concentrations also increased substantially across the watershed, with post-storm mean values commonly exceeding 20 mg/L and maximum concentrations reaching 41 mg/L, indicating sustained dissolved-phase release and enhanced temporal variability. Recovery trajectories differed by solute: phosphate returned to baseline within weeks, nitrate declined gradually, and sulfate remained elevated throughout the winter. These findings demonstrate that substantial chemical perturbations can occur even in the absence of visible storm impacts, underscoring the importance of event-based, high-resolution monitoring to detect transient but consequential shifts in watershed biogeochemistry. They also highlight the need to better resolve solute-specific pathways that govern nutrient mobilization during extreme rainfall in mixed-use watersheds with legacy nutrient stores and engineered drainage networks. Full article

Rice (Oryza sativa L.) readily accumulates cadmium (Cd), posing dietary exposure risks in populations dependent on rice-based diets. This study investigated how sulfur (S) redox processes regulate Cd mobility in S-deficient, Cd-contaminated paddy soil under waterlogged conditions. A pot experiment was conducted with two S treatments (−S and +S, 30 mg kg⁻¹) throughout the rice growing season. S addition markedly increased pore water S²⁻ concentrations during early growth (tillering) and mid-season (booting) and suppressed the diffusion of SO₄²⁻ from non-rhizosphere to rhizosphere at later stages (filling–maturity). Consequently, Cd in soil pore water was significantly lower in +S than −S treatments at all stages. Sulfur-amended soil showed a redistribution of Cd from labile fractions (exchangeable and carbonate-bound) to more stable fractions (Fe/Mn oxide-bound). Sulfur application also altered the rhizosphere microbiome: the relative abundance of sulfate-reducing bacteria (SRB) increased at the booting and filling stages, while sulfur-oxidizing bacteria (SOB) became more dominant at maturity. Additionally, +S enhanced Cd sequestration on rice root iron plaque by 32–67% during the grain-filling and maturity stages compared to −S. Throughout the rice growing period, redox-driven shifts in the S²⁻/SO₄²⁻ ratio emerged as a key control on Cd behavior, with low pe + pH (strongly reducing conditions) promoting Cd sulfide precipitation and high pe + pH (more oxidizing conditions) causing Cd remobilization. Full article

This paper presents a comprehensive characterization of bottom ash generated during biomass combustion in fluidized boilers, with a focus on its potential use in a circular economy. Two biomass bottom ash samples (BBA 1 and BBA 2) from commercial combined heat and power plants were tested. The scope of this study included the determination of chemical composition, phase composition, and leachability testing of selected impurities. The results showed that the bottom ashes tested are calcium silicate materials with varying proportions of calcium phases (anhydrite, portlandite, and calcite) and silica phases (quartz), depending on the type of biomass and combustion technology. Thermal analysis confirmed the presence of characteristic dehydration, decarbonation, and polymorphic transformations of quartz, with a low organic content. Leachability tests showed low mobility of most trace elements and heavy metals, with increased solubility of sulfates, chlorides, and alkali ions, typical for fluidized ash. The concentrations of As, Cd, Cr, Cu, Pb, Zn, and Hg in the eluates were low or below the limit of quantification, indicating the favorable chemical stability of the tested waste. The results obtained suggest that bottom ashes from biomass combustion in fluidized boilers may be a promising secondary raw material for engineering applications, especially in binding materials and bonded layers, and potentially also in selected agricultural applications, provided that the contents of sulfates, chlorides, and pH are controlled. Full article

Many polar compounds of biochemical and pharmaceutical relevance exhibit low retention in reversed-phase liquid chromatography (RPLC), making their separation challenging. While hydrophilic interaction liquid chromatography (HILIC) columns are commonly used for such analyses, they require mobile phases with high organic solvent content. This work explores an alternative approach using RPLC with conventional C18 columns and mobile phases containing low percentages of acetonitrile, along with small amounts of the surfactant sodium dodecyl sulfate (SDS). This combination significantly enhances the retention of highly polar compounds. When the SDS concentration is sufficiently low, below the critical micellar concentration in water (8 mM), the retention increase follows a linear pattern. The retention behavior of polar compounds with different properties (nucleosides, methylxanthines, sulfonamides, and the diuretic hydrochlorothiazide) is examined using mobile phases in the submicellar region, with SDS concentrations ranging from 0 to 0.3 mM, acetonitrile contents between 10 and 20% (v/v), and temperatures varying from 25 to 55 °C. Changes in peak half-widths are also analyzed. Since SDS adsorbs onto the stationary phase, modifying its surface, the equilibration time has been investigated as a critical factor affecting retention reproducibility, influenced by the SDS concentration, acetonitrile content, and temperature. The results emphasize the need for complete equilibration to ensure reliable and consistent results. Full article

Application of wheat straw could contribute to a sulfur-driven reduction in cadmium (Cd) bioavailability under reducing conditions induced by organic matter degradation. A pot experiment was conducted in organic matter deficient paddy soil under waterlogged conditions to assess the effects of sulfur (S, 30 mg kg⁻¹), wheat straw (W, 1.0%), and their combination (WS) on Cd availability and accumulation in rice (Oryza sativa L.). Sulfur application alone increased Cd uptake in rice, whereas straw addition significantly reduced Cd accumulation, with WS achieving the greatest reduction. The mitigating effect was attributed to CdS precipitation and co-precipitation with FeS/FeS₂ under straw amendment, as well as enhanced iron plaque formation on roots, which restricted Cd uptake. In contrast, in OM-deficient soil, sulfate promoted Cd mobilization in pore water due to limited electron supply for sulfate reduction. Compared with other sulfur forms, sulfate is more readily absorbed by rice, thereby synergistically enhancing Cd uptake by rice and promoting Cd translocation in different rice tissues. However, straw amendment supported reduction in sulfate, reducing Cd uptake by rice compared with S supplement alone. Overall, wheat straw amendment enhanced sulfur-mediated immobilization of Cd and effectively decreased Cd accumulation in rice. Full article

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants that tend to accumulate in solid matrices such as sewage sludge, raising concerns regarding their fate and potential ecological risks. This study aimed to develop and validate a robust analytical method for the accurate determination of PFAS in dehydrated sludge. A liquid chromatography–tandem mass spectrometry (LC–MS/MS) method was optimized for 28 PFAS, including perfluoroalkyl carboxylic acids (PFCAs) and sulfonic acids (PFSAs). Solid–liquid extraction with basic methanol was followed by cleanup using a cartridge packed with ferrite and sodium sulfate to remove moisture and particulate interferences. Chromatographic separation was performed with an Avantor^® ACE^® PFAS Delay column coupled to an Agilent triple quadrupole MS operating in negative electrospray ionization mode. The method achieved excellent sensitivity (MDL < 0.02 µg/g dry weight for most compounds), satisfactory precision (RSD < 15%), and recoveries between 80–118%. Optimization of mobile phase additives, gradient conditions, and MS parameters enhanced chromatographic resolution and signal-to-noise ratio. The validated method demonstrates high reliability for PFAS determination in complex solid matrices and can be applied as a valuable tool for environmental monitoring and risk assessment of sludge management practices. Full article

The role of sedimentary heterogeneity in reactive transport processes is becoming increasingly important as closed open-pit lignite mines are converted into post-mining lakes or pumped hydropower storage reservoirs. Flooding of the open pits introduces constant oxygen-rich inflows that reactivate pyrite oxidation within internal mine dumps. A reactive transport model coupling groundwater flow, advection–diffusion–dispersion, and geochemical reactions was applied to a 2D cross-section of a water-saturated mine dump to determine the processes governing pyrite oxidation. Spatially correlated fields representing permeability and pyrite distributions were generated via exponential covariance models reflecting the end-dumping depositional architecture, supported by a suite of scenarios with systematically varied correlation lengths and variances. Simulation results covering a time span of 100 years quantify the impact of heterogeneous permeability fields that result in preferential flow paths, which advance tracer breakthrough by ~15 % and increase the cumulative solute outflux up to 139 % relative to the homogeneous baseline. Low initial pyrite concentrations (0.05 wt %) allow for deeper oxygen penetration, extending oxidation fronts over the complete length of the modeling domain. Here, high initial pyrite concentrations (0.5 wt %) confine reactions close to the inlet. Kinetic oxidation allows for more precise simulation of redox dynamics, while equilibrium assumptions substantially reduce the computational time (>10×), but may oversimplify the redox system. We conclude that reliable risk assessments for post-mining redevelopment should not simplify numerical models by assuming average homogeneous porosity and mineral distributions, but have to incorporate site-specific spatial heterogeneity, as it critically controls acid generation, sulfate mobilization, and the timing of contaminant release. Full article

High Mobility Group Box 1 (HMGB1) is a central pro-inflammatory mediator released from damaged or stressed cells, where it activates receptors such as the Receptor for Advanced Glycation Endproducts (RAGE). Dendritic polyglycerol sulfate (dPGS), a hyperbranched polyanionic polymer, is known for its anti-inflammatory activity. In this study, we examined how dPGS modulates HMGB1-driven signaling in RAW 264.7 macrophages and human microglia. Recombinant human HMGB1 expressed in Escherichia coli (E. coli) was purified by nickel-nitrilotriacetic acid (Ni-NTA) and heparin chromatography. Proximity ligation assays (PLA) revealed that dPGS significantly disrupted HMGB1/RAGE interactions, particularly under lipopolysaccharide (LPS) stimulation, thereby reducing inflammatory signaling complex formation. This correlated with reduced activation of the nuclear factor kappa B (NF-κB) pathway, demonstrated by decreased nuclear translocation and transcriptional activity. Reverse transcription polymerase chain reaction (RT-PCR) and quantitative real-time PCR (RT-qPCR) showed that dPGS suppressed HMGB1- and LPS-induced transcription of tumor necrosis factor alpha (TNF-α), interleukin-6 (IL-6), monocyte chemoattractant protein-1 (MCP-1), cyclooxygenase-2 (COX-2), and inducible nitric oxide synthase (iNOS). Enzyme-linked immunosorbent assay (ELISA) and Griess assays confirmed reduced TNF-α secretion and nitric oxide production. Electron paramagnetic resonance (EPR) spectroscopy further showed that dPGS altered HMGB1/soluble RAGE (sRAGE) complex dynamics, providing mechanistic insight into its receptor-disruptive action. Full article

Fine particulate matter (PM_2.5; aerodynamic diameter ≤ 2.5 µm) remains a challenging policy for industrialized coastal regions throughout East Asia. In this study, we present a multi-year chemical characterization of PM_2.5 and identify key factors contributing to extreme pollution events in Dangjin, a heavy-industry hub on Korea’s west coast. Between August 2020 and March 2024, 24-h gravimetric filters (up to n = 245; 127–280 valid analyses depending on constituent) were collected twice weekly in winter–spring and weekly in summer–autumn. Meteorological data and 48-h backward HYSPLIT trajectories guided source interpretation. The mean PM_2.5 concentration was 26.22 ± 15.29 µg/m³ (4.74–95.31 µg/m³). The mass was highest in winter (30.83 µg/m³). Secondary inorganic ions constituted 60.3% of the aerosol, with nitrate comprising 29.7%. A nitrate-to-sulfate ratio of 1.94 indicated a stronger influence from mobile NO_x emissions compared to that from coal combustion. The trajectory analysis showed north-easterly transport from Eastern China, followed by local stagnation, which promoted rapid ammonium-nitrate formation. Regional transport contributes to severe PM_2.5 episodes, with their magnitude increased by local NO_x and NH₃ emissions. Our findings suggest that effective mitigation strategies in coastal industrial corridors require coordinated control of long-range transport and domestic measures focused on vehicles and ammonia-rich industries. Full article

Tetrahydroprotoberberine alkaloids (THPBs) are bioactive natural products bearing stereogenic centers that frequently exhibit enantiomer-specific pharmacological effects. Xylopinine (XPN), a representative THPB, shows cytotoxic, antimicrobial, and antimalarial activity in vitro, and displays pronounced stereoselectivity in vivo, with the naturally occurring (S)-enantiomer emphasizing the need for reliable enantioselective analysis. In this study, we present the synthesis of racemic XPN from norlaudanosine, and its first comprehensive cyclodextrin-assisted capillary electrophoresis screening dedicated to the enantioseparation of XPN. Sulfated- and sulfobutyl-ether-β-cyclodextrin (S-β-CyD, SBE-β-CyD) provided efficient resolution (R_s > 3), while heptakis-(6-deoxy-6-(2-carboxyethyl)thio)-β-CyD (subetadex, SBX) yielded outstanding separation (R_s > 9). The enantiomer migration order was consistently R,S, except when using SBE-β-CyD, which showed the inverse sequence. Chiral HPLC using a Chiralpak AD column in polar organic mode with methanol modified with 0.1% diethylamine as mobile phase enabled the semi-preparative isolation of XPN enantiomers, with the (S)-enantiomer exceeding 95% purity. The absolute configuration was confirmed by circular dichroism spectroscopy. ¹H NMR titration and 2D rotating-frame nuclear Overhauser effect correlation spectroscopy (ROESY) consistently revealed multi-site recognition of XPN by SBX, supporting the inclusion of both aromatic rings (A and D). Full article

The behavior of S and Cs during the alternate adsorption of each adsorbate on the Ni(100) surface is studied at room and elevated temperatures by means of low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), thermal desorption spectroscopy (TDS) and work function (WF) measurements. For Cs deposition on the S-covered Ni(100) surface, the presence of sulfur increases the binding energy and the maximum amount of adsorbed cesium, as happens with other alkalis too. The first Cs overlayer is disordered, while the second strongly interacts with S with a tendency toward a Cs_xS_y surface compound formation. This interaction causes the gradual demetallization of the Cs overlayer with the increasing S coverage in the underlayer. When the Cs_xS_y stoicheometry is complete, however, subsequent Cs deposition forms an independent rather metallic overlayer. When the sulfated covers the surface, S(0.5ML)/Ni(100) is preheated to 1100 K, the S-Ni bond strengthens and S-Cs interaction correspondingly weakens to a degree that the S underlayer retains a periodic structure on the Ni substrate. This behavior indicates that the preheated S/Ni(100) surface is passivated to a degree against Cs with reduced mobility of sulfur adatoms. Differently, when S is adsorbed on the Cs-covered Ni(100) surface at room temperature, sulfur adatoms diffuse underneath the Cs overlayer to interact with the nickel substrate and form the same structural phases as on a clean surface. During that process, the sticking coefficient of sulfur remains constant regardless of the amount of pre-deposited cesium. The presence of Cs, however, increases the amount of S that can be deposited on the Ni substrate, probably in favor of the Cs_xS_y compound formation, which demetallizes the surface independent of the sequence of adsorption. Full article