Search Results (9,309)

Size-exclusion chromatography (SEC) or gel-permeation chromatography (GPC) is an essential tool for determining the molecular weight and polydispersity of water-soluble polymers, including biopolymers used in hydrogels, sealants, bioinks, and other biomedical materials. However, aqueous SEC of polyelectrolytes, i.e., charged polymers, is often complicated by non-size interactions among polymer chains, porous column beads, pore surfaces, frits, tubing, and mobile phase. Salt addition to eluent is commonly used to screen these interactions, but the minimum salt concentration required to restore reliable SEC behavior remains poorly defined, and excessive salt may introduce tailing, refractive-index artifacts, deposits, or instrument concerns. In this study, aqueous SEC with refractive index (RI) and right-angle light scattering (RALS) detection was used to evaluate the effect of salt ($\mathrm{N}{\mathrm{a}}_2\mathrm{S}{\mathrm{O}}_4$) concentration on poly(ethylene oxide) (PEO), a nominally neutral reference standard polymer, and sodium alginate as a model anionic biopolymer. PEO retained a single bell-shaped peak across the tested salt range, but its elution volume and SEC/RALS-derived molecular weights varied slightly with salt concentration, showing that even a nominally neutral reference polymer is affected by mobile-phase conditions. Alginate showed much stronger salt dependence: eluent at very low salt concentration produced broad, noisy, and convoluted chromatograms, whereas increasing salt concentration progressively narrowed the main peak. The first condition that produced a clear, approximately symmetric RI/RALS main peak was $6.25\times {10}^{-3} \mathrm{M}$ $\mathrm{N}{\mathrm{a}}_2\mathrm{S}{\mathrm{O}}_4$, identifying it as the minimum effective salt concentration for this alginate/column/instrument system. To rigorously validate these observations, we propose a set of both qualitative and quantitative peak analyses that objectively confirm the optimal mobile-phase conditions. Ultimately, these results provide a practical workflow for identifying the minimum effective salt concentration required for reliable SEC analysis of water-soluble polymers. Full article

In this study, we combine experimental and computational approaches to elucidate a density functional theory (DFT)-derived mechanism for superoxide scavenging by resveratrol, piceatannol, and oxyresveratrol. Using rotating ring–disk electrode (RRDE) hydrodynamic voltammetry, the superoxide radicals are generated in situ, allowing direct measurement of antioxidant activity. Data show that the catechol-containing piceatannol is approximately four times more active than resveratrol, while resveratrol and oxyresveratrol exhibit similar efficiencies, indicating that the additional 2′-OH group in oxyresveratrol has minimal impact. Vitamin C (ascorbic acid) facilitates scavenging by acting as a proton donor for resveratrol, piceatannol, and 4′-OH oxyresveratrol, but it is unable to deprotonate the 2′OH group of oxyresveratrol. The experimental results suggest a superoxide dismutase (SOD)-like mechanism, obtained from energetically feasible DFT calculations, in which these stilbenes convert two superoxide anions into H₂O₂ and O₂, helped by vitamin C. Mechanistically, the first superoxide is reduced by abstracting a hydroxyl-group hydrogen atom, while the second undergoes oxidation via π–π interaction with the aromatic system, releasing O₂. Notably, resveratrol can be regenerated through a catalytic cycle involving vitamin C. These data underscore the SOD-mimicking properties of dietary polyphenols and suggest a need to reevaluate resveratrol’s clinical utility regardless of its low bioavailability. Full article

In this work, an ultrasonic relaxation spectroscopic study of aqueous ammonium Fe(II) sulfate, aqueous ammonium Fe(III) sulfate and the corresponding ternary system has been undertaken. A variety of acoustic parameters including relaxation frequency, relaxation amplitude and speed of sound were determined as a function of solution concentration. In addition, the adiabatic compressibility and the molar volume change during the ionic association in ammonium Fe(II) sulfate and ammonium Fe(III) sulfate aqueous solutions were also estimated from the acoustic data. This approach facilitated a comprehensive characterization of the three systems across different concentrations. In the two binary systems, the presence of an ion association mechanism was identified involving the divalent and trivalent iron ions, with the sulfate anions, respectively. Furthermore, in the ternary system, an internal sphere oxidation–reduction mechanism occurred between the divalent and trivalent iron ions. All ions within each solution play an active role in shaping the structure of water molecules, owing to the prevailing kosmotropic characteristics specific to each solution. The results are examined within the context of the current phenomenological understanding in the field. Full article

Seasonal freeze–thaw cycling progressively rearranges pores and propagates microcracks in silty clay, reducing the reliability of cold-region earthworks. This study evaluated a bio–polymer stabilization strategy combining microbially induced carbonate precipitation (MICP) with anionic polyacrylamide (APAM) to improve mechanical performance and freeze–thaw durability. Six groups were prepared at identical moisture and compaction conditions: water, APAM, and four MICP–APAM groups with bacterial optical densities (OD600) of 0.8, 1.0, 1.2, and 1.4. Unconfined compressive strength, unconsolidated-undrained triaxial compression, ultrasonic pulse velocity, and SEM, TG/DTG, XRD, and FTIR analyses were conducted before and after freeze–thaw cycling. The M1.0-APAM group showed the best overall performance, with UCS values of 1.35 MPa before cycling and 0.89 MPa after nine cycles, together with high shear resistance and ultrasonic velocity. Lower bacterial concentration provided insufficient cementation, whereas higher concentrations promoted non-uniform carbonate deposition, pore heterogeneity, and local stress concentration. Microstructural evidence indicated that OD600 ≈ 1.0 produced a relatively homogeneous network of fine carbonate clusters and polymer-associated films, with calcite formation supported by TG/DTG and XRD. The results show that MICP–APAM treatment enhances silty clay primarily through coordinated mineralization uniformity, pore refinement, and polymer bridging, providing a sustainable stabilization option for seasonally frozen soils. Full article

This research investigates cobalt-based and iron-based coordination polymers as advanced adsorbents for removing nitrate from water, addressing the increasing demand for effective and customizable treatment materials. Both coordination polymers were synthesized through solvothermal methods using terephthalic acid as the organic linker and were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), which verified their crystalline, porous structures and uniform metal dispersion; Fourier-transform infrared spectroscopy (FTIR) was used to analyze surface characteristic functional groups of the samples before and after adsorption. Batch adsorption tests combined with response surface methodology (RSM), based on a Box–Behnken (BBD), were employed to optimize key operating conditions, including adsorbent dose (0.1–0.5 g/L), pH (3–7), and temperature (25–45 °C). Under optimal conditions (pH 3–5, 0.3 g/L, 30–35 °C), the Co-coordination polymer achieved a maximum nitrate removal of 54.1% and an adsorption capacity of 212.8 mg/g, while the Fe-coordination polymer reached 30.5% removal with a capacity of 35.0 mg/g. Kinetic studies were well fitted by the pseudo-second-order (PSO) model for the Co-coordination polymer (R² = 0.992–0.997), indicating chemisorption control, whereas the Fe-coordination polymer exhibited diffusion-driven behavior. The equilibrium data fit the Langmuir model well for both, confirming monolayer adsorption. The findings suggest that the Co-coordination polymer provides superior nitrate removal owing to stronger metal–anion interactions, whereas the Fe-coordination polymer offers more stable but lower adsorption capacity. Full article

Fresh broccoli is highly perishable, exhibiting rapid yellowing and quality deterioration with a short shelf life. In this study, we investigated the effects of nanomaterial-modified atmosphere packaging (MAP) bags with different thicknesses, designated as 2.5C (25 μm) and 4C (40 μm), on the physiological and biochemical changes in broccoli were evaluated during storage at 20 ± 1 °C for 8 days. Results showed that both MAP treatments remarkably delayed floret senescence by inhibiting the rapid color transition from green to yellow, as indicated by alterations in L*, a*, b*, and hue angle values, as well as by suppressing chlorophyll degradation. The 2.5C treatment exhibited a more pronounced effect during storage. MAP treatments helped maintain commercial quality by preserving total phenols and vitamin C (Vc) content, retaining stem firmness and surface glossiness, regulating post-opening respiration rate and reducing water loss. MAP treatments also effectively suppressed the accumulation of superoxide anion (O₂•⁻) and hydrogen peroxide (H₂O₂). Furthermore, MAP treatments enhanced free radical scavenging capacity, as demonstrated by DPPH and ABTS assays and the O₂•⁻ scavenging rate in broccoli. These results indicate that MAP treatment with an appropriate thickness (e.g., 2.5C) effectively inhibits excessive ROS production and enhances antioxidant capacity, thereby delaying floret chlorophyll degradation and senescence. This study provides a foundation for developing effective and green preservation strategies using physical MAP treatments for fresh broccoli. Full article

Per- and polyfluoroalkyl substances (PFASs) are persistent environmental contaminants whose mobility in soil and groundwater is strongly controlled by adsorption and desorption processes. In saturated clay-rich soils, these processes are complex because PFASs interact with hydrated mineral surfaces, organic matter, metal oxides, exchangeable cations, and pore-water constituents. This review synthesizes the current literature on PFAS adsorption and desorption in saturated soils, with an emphasis on clay mineralogy, mineral–water interfaces, pore-water chemistry, and electrochemical double layer (EDL) effects. PFAS retention is influenced by molecular properties such as chain length, functional head group, and charge state, as well as soil properties such as organic carbon content, clay mineral type, surface charge, cation exchange capacity, and Fe/Al oxide content. Longer-chain PFASs and sulfonate-based compounds generally show stronger retention, while shorter-chain PFASs tend to remain more mobile. This review focuses particularly on how an EDL affects PFAS behavior in saturated clay systems. Unlike dry clay surfaces, saturated clay surfaces are covered by structured water, exchangeable ions, and diffuse counterion layers. These hydrated interfacial conditions influence how closely anionic PFASs can approach negatively charged clay surfaces, how dissolved cations reduce electrostatic repulsion or promote cation-mediated binding, and how effectively short-range interactions such as hydrophobic association, van der Waals forces, hydrogen bonding, and surface association contribute to adsorption. Desorption is also emphasized because adsorption does not necessarily represent permanent immobilization. Changes in pH, ionic strength, cation composition, dissolved organic matter, or competing solutes can weaken retention and promote PFAS release. Overall, PFAS mobility in saturated clay-rich soils should be interpreted as a coupled interfacial process rather than simple partitioning to soil solids. Future work should better connect molecular-scale mechanisms, EDL behavior, adsorption–desorption experiments, and saturated transport studies to improve predictions of PFAS retention and long-term groundwater release. Full article

This study investigates the feasibility of recycling scallop shells as a partial substitute for natural coarse aggregates in concrete at replacement rates of 20%, 30%, and 40% by mass. The originality of the work lies in combining conventional mechanical and durability tests with a six-month environmental monitoring protocol under simulated rainfall and an end-of-life regulatory interpretation of chemical release. Processed shells were used as a 2/20 mm coarse fraction and characterized by a density of 2713 kg/m³, a water absorption of 2.93%, and a Los Angeles coefficient of 15.1. At 28 days, compressive strength decreased from 33.7 MPa for the reference concrete to 27.9 MPa, 28.1 MPa, and 26.7 MPa for SS20, SS30, and SS40, respectively. Water-accessible porosity increased from 7.8% to 9.9%, and carbonation depth after 70 days increased from 6.2 mm to 12.8 mm at 40% shell replacement. In contrast, chloride ion migration decreased from 19.0 × 10⁻¹² m²/s for the reference concrete to 17.4, 16.3, and 12.1 × 10⁻¹² m²/s at 90 days for SS20, SS30, and SS40, respectively. Environmental monitoring showed low runoff concentrations for anions and trace metals, all below the French regulatory thresholds considered in this work. Under the conditions of this study, shell replacement up to 30% appears technically feasible for non-structural or lightly loaded applications, while the environmental behavior remained compatible with an inert end-of-life classification. Full article

The demineralization of tooth enamel is the primary consequence of dental caries, leading to cavities and finally tooth loss. Erosive tooth wear from acidic beverages and food is another factor that degrades enamel. In both cases, an acidic environment leads to etching and the final dissolution of tooth mineral, i.e., hydroxyapatite. Here, this process is discussed from a chemical perspective, taking into account the solubility of calcium phosphate and the presence of the pellicle (protein layer) and plaque (bacterial biofilms), which both affect the dissolution rate. While low pH is definitely decisive, calcium-binding ligands (e.g., acid anions, proteins) contribute to dissolution by removing calcium ions from the equilibrium. This is an important effect in the oral cavity where the concentration of biomolecules is high. The situation is complicated by the fact that the composition of saliva and the oral microbiome vary considerably between individuals. The state of current knowledge on the demineralization of enamel is summarized and discussed, also in the context of approaches to prevent dental caries and erosive tooth wear. Full article

Developing cost-effective alternatives to platinum-based catalysts remains paramount for commercializing anion exchange membrane fuel cells (AEMFCs). We report a metal-free nitrogen-doped carbon catalyst derived from a rationally designed polyurea–polyimine copolymer that outperforms commercial 20 wt% Pt/C in superior relative durability and methanol tolerance. Strategic integration of polyurea’s pore-forming capability with polyimine’s thermal stability enabled the synthesis of a catalyst (NC-1000N) featuring ultrahigh surface area (1276.5 m² g⁻¹), optimal nitrogen speciation (20.5% pyridinic-N, 45.3% graphitic-N), and enhanced graphitization, which improves the electrical conductivity of catalysts. NC-1000N exhibited exceptional oxygen reduction performance with an onset potential of 0.96 V, almost four-electron selectivity (n = 3.87), a medium Tafel slope (105 mV dec⁻¹), and minimal charge transfer resistance (46.74 Ω). When evaluated in single-cell AEMFCs, NC-1000N delivered a peak power density of 372.1 mW cm⁻², which is 26% higher than Pt/C at equivalent loading, while demonstrating superior stability (94.8% retention after 7 h) and complete methanol tolerance. Systematic pyrolysis temperature optimization (800–1000 °C) revealed critical structure–property relationships governing catalyst evolution from disordered precursor to highly graphitic, nitrogen-enriched carbon with precisely engineered active sites. This work establishes polymer-derived carbons and provides design principles for scalable synthesis of high-performance metal-free electrocatalysts for sustainable energy conversion technologies. Full article

Adsorption is a promising technology for phosphate removal to alleviate eutrophication. In this study, thermally modified calcium aluminate decahydrate (TCAH) was prepared via low-temperature thermal treatment of calcium aluminate decahydrate (CAH₁₀) to develop a cost-effective and high-performance phosphate adsorbent. The optimal modification temperature was determined to be 120 °C, which reduced the crystallinity of CAH₁₀, enhanced its porosity, and induced the formation of amorphous calcium aluminate phases. Batch adsorption experiments showed that TCAH exhibited a maximum adsorption capacity of 199.80 mg P/g at 25 °C. The adsorption kinetics followed the pseudo-second-order model, while the adsorption isotherms were well fitted by the Redlich–Peterson model. TCAH maintained high removal efficiency over a wide pH range of 3.0–11.0 and showed high selectivity against common coexisting anions. Characterizations using SEM-EDS, XRD, FTIR and XPS suggested that phosphate removal by TCAH was dominated by synergistic amorphous precipitation and inner-sphere complexation. In tests with real phosphorus-releasing liquor derived from excess sludge, TCAH achieved nearly complete phosphate removal at a dosage of 5 g/L within 6 h. Owing to its readily available raw materials, low preparation temperature, and outstanding phosphate capture performance, TCAH is a promising candidate for efficient phosphate capture and recovery from wastewater. Full article

The demand for sustainable, high-performance biomaterials has driven intense research towards natural polysaccharide hydrogels. Accordingly, this study aimed to synthesize novel starch-based hydrogel materials, considering their inherent hydrogel-forming capabilities together with diverse potential applications (e.g., pharmaceuticals, medicine, and the cleaning application for the artifacts). To obtain hydrogels with enhanced mechanical and physico-chemical properties, starch was combined with other polymeric species (i.e., alginate, polyvinyl alcohol, and polyvinylpyrrolidone), and a gelling process was induced by using calcium cations or borate anions. Two distinct hydrogels (named S-Ca and S-SB, respectively) were prepared and characterized by a range of instrumental and experimental techniques. The assessed properties included water and solvent resistance, equilibrium water content, water-releasing capacity, morphology and microstructural features with their composition by SEM-EDS analysis, and mechanical properties (tensile strength, elasticity, Young’s modulus, and hardness). The results indicated that the investigated hydrogels exhibited suitable properties for a variety of applications, including surface cleaning processes in the field of cultural heritage conservation. For instance, they showed equilibrium water content (between 80 and 90%) comparable with other hydrogels commonly used as cleaning tools (e.g., agar and p(HEMA)/PVP) and quite low water-releasing capacity (between 10 and 17 mgcm⁻²). Moreover, the S-SB hydrogel displayed distinctly better tensile strength and elongation at break than hydrogel prepared in the presence of Ca²⁺ (S-Ca). Notably, S-SB experienced considerable elasticity improvement after freezing–thawing cycles, as indicated by a decrease in tensile strength (from 275 to 102 kPa) and an increase in elongation at break (from 121 to 275%). However, it should be noted that the hydrogel selection depends on the requirements of the target application, as different processes demand materials with distinct characteristics. Hence, both S-Ca and S-SB hydrogels were tested as cleaning tools for the removal of artificially aged acrylic coating (i.e., Paraloid B-72) from the surface of marble and wood specimens, respectively. The tests provided positive results, as aged coating was satisfactorily removed by applying the hydrogels loaded with a nanostructured emulsion (NSE). These novel starch-based hydrogels demonstrate significant potential as high-performance alternatives to conventional hydrogel systems currently used in conservation science as well as in other industrial applications. Full article

Environmental pollution by polycyclic aromatic hydrocarbons (PAHs) is a serious environmental problem. One of the effective methods of cleaning the environment from these toxicants is the use of sorbents based on clay minerals. Special organo-mineral, bio-mineral and bio-organo-mineral complexes were obtained. Organo-mineral complexes (organoclays) were synthesized on the basis of Na-bentonite and anionic, amphoteric and nonionic surfactants. Bio-mineral and bio-organo-mineral complexes were produced by inoculating bentonite and organoclays with a consortium of bacteria. The adsorption characteristics of the complexes to benzopyrene and naphthalene were studied. Modification of bentonite with various types of surfactants leads to a significant increase in the percentage adsorption of both benzopyrene and naphthalene, with benzopyrene being more so. All bio-organo-mineral complexes adsorb more benzopyrene than pure bentonite and the bentonite + bacteria complex. In most cases, this pattern is also characteristic of naphthalene adsorption. Organoclay complexes with bacteria adsorb PAHs in greater quantities than organoclays, typically at the average concentrations of benzopyrene and naphthalene used (30–60 μg mL⁻¹) and when modified with individual surfactants. Based on the determination coefficients, the adsorption of benzopyrene and naphthalene by all studied sorbents is best described by the Langmuir equation. The maximum (limiting) adsorption of benzopyrene by all organo-mineral complexes (organoclays) exceeds the maximum adsorption of benzopyrene by bentonite. Modification of bentonite with surfactants may not change, decrease, or increase the maximum adsorption of naphthalene compared to the original bentonite, depending on the surfactant used. Colonization of the organoclay surface by bacteria, with rare exceptions, results in a decrease in the maximum adsorption values of benzopyrene and naphthalene compared to organoclay, or has no effect at all. Full article

Aqueous zinc–manganese dioxide (Zn–MnO₂) batteries are undergoing a paradigm shift from traditional ion-insertion mechanisms to a reversible deposition/dissolution process. By leveraging a two-electron transfer (Mn²⁺/MnO₂), this electrolytic system achieves a high theoretical capacity of 616 mAh g⁻¹ and a theoretical operating voltage of 1.99 V. However, the accumulation of dead Mn, electrically isolated inactive phases, and dynamic interfacial pH fluctuations remain critical barriers to cycle life and practical energy density. This review systematizes a trinitarian strategy to overcome these bottlenecks, focusing on interfacial engineering, redox mediator-assisted recovery, and advanced electrode architectures. We evaluate how anion engineering and pH-buffering stabilize reaction pathways, and how diverse mediators (e.g., halogens, metal ions, and organic molecules) chemically rescue inactive manganese. Furthermore, we examine the integration of 3D carbon networks and low-cost hybrid electrodes to sustain high-areal-capacity deposition. To elucidate these complex mechanisms, we highlight multiscale analytical approaches combining synchrotron X-ray techniques and density functional theory (DFT). Finally, we outline a roadmap for applications ranging from grid-scale flow batteries to flexible wearable electronics. This work provides a comprehensive perspective on realizing sustainable, safe, and high-performance zinc-based energy storage. Full article

Metanephrine (MN) and normetanephrine (NMN) are critical biomarkers for neuroendocrine tumors (pheochromocytoma and paraganglioma). Following our previous development of a molecularly imprinted solid-phase extraction (MISPE) sorbent for urine analysis, this study evaluated MISPE coupled with HILIC-MS/MS for determining metanephrines in human plasma. Unlike conventional phases, the novel polymer selectively binds analytes as in situ-generated anions via quaternary alkylammonium groups in hydroxide form, ensuring accurate extraction from just 25 µL of plasma. Validated per U.S. FDA guidelines, the assay showed good intra- and interday precision (CV < 10.8%), accuracy (bias < −10.6%) and excellent linearity (R² > 0.99) across pathological ranges (184.3–877.8 ng/L for MN; 174.8–923.0 ng/L for NMN), with low relative standard errors (<6.9%). Excellent selectivity was demonstrated in the presence of structurally close analogs (catecholamines, DOPA and its derivatives). Compared with commercial WCX, the sorbent yielded cleaner extracts, significantly reducing the phospholipid interference. Although lower limits of quantification (92.2 ng/L MN; 87.4 ng/L NMN) slightly exceeded healthy upper thresholds, the method has potential for use in specific clinical scenarios with pronounced biomarker elevations: diagnosis of pheochromocytoma/paraganglioma, monitoring post-treatment metanephrine decline, and tracking tumor-induced hypertensive crises in emergencies. This accessible protocol forms a solid foundation for advanced diagnostics. Full article