Search Results (363)

Biothiols, including cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), are crucial for physiological regulation and their imbalance poses severe health risks. Herein, we developed a pH-responsive liquid crystal (LC)-based sensing platform for detection of biothiols by doping 4-n-pentylbiphenyl-4-carboxylic acid (PBA) into 4-n-pentyl-4-cyanobiphenyl (5CB). Urease catalyzed urea hydrolysis to produce OH⁻, triggering the deprotonation of PBA, thereby inducing a vertical alignment of LC molecules at the interface corresponding to dark optical appearances. Heavy metal ions (e.g., Hg²⁺) could inhibit urease activity, under which condition LC presents bright optical images and LC molecules maintain a state of tilted arrangement. However, biothiols competitively bind to Hg²⁺, the activity of urease is maintained which enables the occurrence of urea hydrolysis. This case triggers LC molecules to align in a vertical orientation, resulting in bright optical images. This pH-driven reorientation of LCs provides a visual readout (bright-to-dark transition) correlated with biothiol concentration. The detection limits of Cys/Hcy and GSH for the PBA-doped LC platform are 0.1 μM and 0.5 μM, respectively. Overall, this study provides a simple, label-free and low-cost strategy that has a broad application prospect for the detection of biothiols. Full article

The aim of our work is to theoretically model the conversion of C6 and C5 carbohydrates derived from lignocellulosic biomass waste into C1–C5 carboxylic acids such as levulinic, oxalic, lactic, and formic acids. Understanding the mechanism of these processes will provide the necessary knowledge to better plan the structure of zeolite. In this article, we focus on the theoretical modeling of two carbohydrates, representing C5 and C6, namely xylose and fructose, into levulinic acid (LE) and formic acid (FA). The modeling was carried out with the participation of Na-BEA zeolite in a hierarchical form, due to the large size of the carbohydrates. The density functional theory (DFT) method (StoBe program) was used, employing non-local generalized gradient-corrected functions according to Perdew, Burke, and Ernzerhof (RPBE) to account for electron exchange and correlation and using the nudged elastic band (NEB) method to determine the structure and energy of the transition state. The modeling was performed using cluster representations of hierarchical Na-Al₂Si₁₂O₃₉H₂₃ and ideal Al₂Si₂₂O₆₄H₃₄ beta zeolite. However, to accommodate the size of the carbohydrate molecules in reaction paths, only hierarchical Na-Al₂Si₁₂O₃₉H₂₃ was used. Sodium ions were positioned above the aluminum centers within the zeolite framework. Full article

As a bridge for human–machine interaction, the performance improvement of sensors relies on the in-depth understanding of ion transport mechanisms. This study focuses on the surface effect of resistive gel sensors and designs a polyacrylic acid/ferric ion hydrogel (PAA/Fe³⁺) gas flow sensor. Prepared by one-pot polymerization, PAA/Fe³⁺ forms a three-dimensional network through the entanglement of crosslinked and uncrosslinked PAA chains, where the coordination between Fe³⁺ and carboxyl groups endows the material with excellent mechanical properties (tensile strength of 80 kPa and elongation at break of 1100%). Experiments show that when a gas flow acts on the hydrogel surface, changes in surface humidity alter the density of the network structure, thereby regulating ion migration rates: the network loosens to promote ion transport during water absorption, while it tightens to hinder transport during water loss. This mechanism enables the sensor to exhibit significant resistance responses (ΔR/R₀ up to 0.55) to gentle breezes (0–13 m/s), with a response time of approximately 166 ms and a sensitivity 40 times higher than that of bulk deformation. The surface ion transport model proposed in this study provides a new strategy for ultrasensitive gas flow sensing, showing potential application values in intelligent robotics, electronic skin, and other fields. Full article

Poly(acrylic acid) (PAA) and hydroxypropylcellulose (HPC) hydrogels were synthesized in the absence of a crosslinker. Chemical crosslinking between PAA and HPC was demonstrated through free radical polymerization by a precipitation reaction in acetone as the solvent. These hydrogels exhibited smaller swelling ratios (1 to 5 g H₂O/g) than homo PAA hydrogels synthesized in water as the solvent. They were swollen in a 0.1 M NaOH solution and subsequently used to remove Ni²⁺ ions from aqueous solutions with concentrations ranging from 1000 to 4000 ppm. The absorption capacity of these hydrogels ranged from 91 to 340 mg of Ni²⁺/g in a rapid 1 h process, and from 122 to 435 mg of Ni²⁺/g in a 24 h process, demonstrating an improvement in Ni²⁺ absorption compared to previously reported hydrogels. The colored 1000 and 2000 ppm Ni²⁺ solutions became clear after treatment, while the PAA-HPC hydrogels turned green due to the uptake of Ni²⁺ ions, which were partially chelated by carboxylate groups as nickel polyacrylate and partially precipitated as Ni(OH)₂, resulting in an average absorption efficiency of 80%. The hydrogel was able to release the absorbed Ni²⁺ upon immersion in an HCl solution, with an average release percentage of 76.4%, indicating its potential for reuse. These findings support the use of PAA-HPC hydrogels for cleaning Ni²⁺-polluted water. The cost of producing 1 g of these hydrogels in laboratory conditions is approximately 0.2 USD. Full article

In this study, 3-chlorothiophene-2-carboxylic acid (HL) was used as a main ligand to successfully synthesize four novel complexes: [Cu(L)₂(Py)₂(OH₂)₂] (1), [Co(L)₂(Py)₂(OH₂)₂] (2) (Py = pyridine), [{Ni(L)₂(OH₂)₄}₂{Ni(L)(OH₂)₅}]L•5H₂O (3), and [{Co(L)₂(OH₂)₄}₂{Co(L)(OH₂)₅}]L•5H₂O (4). All four compounds were identified by elemental analysis and ESI mass spectrometry, and subsequently characterized by IR spectroscopy, UV-visible diffuse reflectance spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography, and cyclic voltammetry. X-ray analyses revealed that complexes 1 and 2 exhibit a centrosymmetric pseudo-octahedral coordination geometry; the copper (II) and cobalt (II) metal ions, respectively, are located at the crystallographic center of inversion. The coordination sphere of the copper (II) complex is axially elongated in accordance with the Jahn–Teller effect. Intriguingly, for charge neutrality, compounds 3 and 4 crystallized as three independent mononuclear octahedrally coordinated metal centers, which are two $\left[\mathrm{M}{\mathrm{L}}_2{\left({\mathrm{O}\mathrm{H}}_2\right)}_4\right]$ complex molecules and one ${\left[\mathrm{M}\mathrm{L}{\left({\mathrm{O}\mathrm{H}}_2\right)}_5\right]}^{+}$ complex cation (M = ${\mathrm{N}\mathrm{i}}^{\mathrm{I}\mathrm{I}}$ and ${\mathrm{C}\mathrm{o}}^{\mathrm{I}\mathrm{I}}$, respectively), with the ligand anion ${\mathrm{L}}^{-}$ serving as the counter ion. The anticancer activities of these complexes were systematically assessed on human leukemia K562 cells, lung cancer A549 cells, liver cancer HepG2 cells, breast cancer MDA-MB-231 cells, and colon cancer SW480 cells. Among them, complex 4 shows significant inhibitory effects on leukemia K562 cells and colon cancer SW480 cells. Full article

Novel peptide-zinc chelates (DSPs-Zn) with a zinc content of 186.94 mg/g were synthesized from deer tendon peptides at pH 6, 60 °C, 60 min, and peptide-zinc mass ratio of 1:3. Ultraviolet-visible absorption spectroscopy (UV) and Fourier transform infrared spectroscopy (FTIR) demonstrated that the chelation sites of the deer tendon polypeptides (DSPs) with zinc ions were located at the carboxyl oxygen and amino nitrogen atoms of the peptides. Amino acid analysis showed that aspartic acid, glutamic acid, lysine, and arginine play important roles in the chelation process. In vitro simulated gastrointestinal digestion studies showed that DSPs-zinc exhibited higher stability than zinc sulfate and zinc gluconate in the pH range 2–8 and in a simulated gastrointestinal digestion environment. The above experimental results suggest that DSPs-Zn has the potential to be used as a novel zinc nutritional supplement. Full article

The limited understanding of intermolecular interactions in deep eutectic solvents (DESs) has restricted their rational design and broader application. In this study, a series of hydrophobic DESs (HDESs) were prepared using lidocaine as the hydrogen bond acceptor and various carboxylic acids as hydrogen bond donors. Their physicochemical properties, including density, viscosity, and thermal stability, were systematically characterized. Interactions between components were evaluated through excess molar volume, viscosity deviation, and Grunberg–Nissan parameters. Strong hydrogen bonding between lidocaine and carboxylic acids was confirmed, which weakened with increasing alkyl chain length of the acids. Furthermore, as the acid content in the mixture increased, lidocaine’s ability to disrupt the intrinsic hydrogen-bonding network of the carboxylic acids decreased, thereby weakening the hydrogen bonding interactions between the components. The extraction capability of the HDESs for cobalt ions was evaluated in aqueous systems. Cobalt, a key material in lithium-ion batteries and advanced alloys, is in rising demand due to clean energy development. The lidocaine/decanoic acid (1:2) system exhibited nearly 100% extraction efficiency, surpassing conventional extractants. The hydrophobic nature of the HDESs facilitated effective phase separation and reduced solvent loss. These findings provide theoretical insights and design principles for developing high performance HDESs tailored for environmentally friendly metal recovery, particularly in battery recycling and treatment of industrial wastewater. Full article

Iron deficiency is a global health issue, making the development of novel iron supplements to enhance iron absorption critically important. In this study, low molecular weight donkey-hide gelatin peptides (LMW DHGP) were enzymatically hydrolyzed from donkey-hide gelatin. Experimental results demonstrated that the iron chelating capacity of LMW DHGP reached 249.98 μg/mg. Key amino acids (Asn, Gly, Cys, Lys) may participate in chelation. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis showed rough, porous amorphous structures of LMW DHGP-iron complexes. The results of circular dichroism spectroscopy (CD) indicated that the self-assembly of LMW DHGP-iron complexes appears to be primarily mediated by peptide α-helical structural conformations. Fourier transform infrared (FTIR) spectroscopy further indicated that the interaction between LWM DHGP and Fe²⁺ likely occurs through carboxyl and amino functional groups. In vitro digestion stability studies demonstrated that LMW DHGP-iron complexes exhibited superior iron ion solubility compared to FeSO₄ in simulated gastrointestinal conditions. PGPAG-iron complexes exhibited the highest antioxidant activity, with scavenging rates of 71.64% (DPPH radical) and 88.79% (ABTS radical). These findings collectively suggest that LMW DHGP-iron complexes possess significant potential as a novel iron supplement in food applications, which provides valuable theoretical insights for the development of innovative iron supplementation strategies. Full article

Catechol-like compounds are found throughout biology in the form of both redox-active and metal-binding functional groups. Within the marine environment, catechol groups are known to coordinate strongly with vanadate and ferric ions, and this binding is regulated through redox mechanisms. While investigating marine melanin formation in vitro, we found that DOPA, a catechol-containing amino acid, reacts with both metals differently when provided with sulfite, a weak reductant, and selenite, a weak oxidant. Both compounds interacted with the DOPA–vanadium complex, but only selenite, the more redox-labile chalcogenide, led to the creation of melanin particulates. When DOPA, vanadate, and selenite are present together, a metal-binding spectra shift and a melanin variant are rapidly observed. This variant was found to form large, elongated filaments with a low carboxylic acid content and a unique electron paramagnetic resonance signature. When compared to enzymatically produced melanin, this chemically synthesized variant was more thermally and biologically inert, exhibiting a lower redox activity. The results demonstrate that the regulation of the redox environment from metal–catechol interactions can help to control both the chemical and physical properties of melanin aggregates, suggesting a scalable and cell- and enzyme-free synthesis pathway for applications that may require inert materials of strict composition. Full article

This study investigates the degradation mechanisms of fiber-reinforced polymer (FRP) matrices in composite insulators under partial discharge (PD) conditions. The degradation products may further cause deterioration of the electrical and chemical resistance (ECR) glass fibers. Using pyrolysis–gas chromatography-mass spectrometry (PY-GC-MS) and high-performance liquid chromatography–tandem mass spectrometry (HPLC-MS-MS), the thermal degradation gas and liquid products of the degraded FRP matrix were analyzed, revealing the presence of organic acids. These acids form when the epoxy resin’s cross-linked bonds break at high temperatures, generating anhydrides that hydrolyze into carboxylic acids in the presence of moisture. The hydrolyzation process is accelerated by hydroxyl radicals produced during PD. The resulting carboxylic acids deteriorate the glass fibers within the FRP matrix by degrading surface coupling agents and reacting with the alkali metal–silica network, leading to the substitution and precipitation of metal ions. Organic acids, particularly carboxylic acids, were found to have a more severe deteriorating effect on glass fibers compared to inorganic acids, with high temperatures exacerbating this process. These findings provide critical insights into the deterioration mechanisms of FRP under operational conditions, offering valuable guidance for optimizing manufacturing processes and enhancing the longevity of composite insulators. Full article

This study reports the synthesis and characterization of four novel rare earth-gallic acid complexes, Sm(Gal)₃·4H₂O, Eu(Gal)₃·4H₂O, Tb(Gal)₃·4H₂O, and Dy(Gal)₃·4H₂O. These complexes were synthesized under optimized conditions (60 °C, pH 4–5) and characterized using the Ln³⁺ elemental content method, infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), mass spectrometry (MS), and fluorescence spectroscopy. IR spectra confirmed the coordination of rare earth ions (Ln³⁺) with gallic acid through carboxylate oxygen atoms. TGA revealed the thermal decomposition pathways, while MS identified the molecular ion peaks and fragmentation patterns. All complexes exhibited strong luminescence under UV excitation, with emission peaks corresponding to characteristic transitions of Sm³⁺, Eu³⁺, Tb³⁺, and Dy³⁺. Biological assays demonstrated significant antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa, with Dy(Gal)₃·4H₂O showing the highest efficacy. Additionally, the complexes displayed inhibitory effects on MCF7 breast cancer cells, with Tb(Gal)₃·4H₂O exhibiting the lowest IC₅₀ value (11.3 µM). These findings suggest that rare earth metal complexes with gallic acid have potential applications in biomedical fields, particularly as antimicrobial and anticancer agents. Full article

The rapid pace of industrialization has led to widespread heavy metal contamination in water and soil, highlighting the need for efficient remediation strategies. Among various approaches, adsorption has proven to be an effective method for treating contaminated environments. Layered double hydroxide (LDH) is frequently used in such applications. However, its adsorption efficiency remains limited. In this study, glutamic acid diacetate tetrasodium salt (GLDA) was incorporated into ZnAl LDH via a straightforward co-precipitation and ion exchange method, yielding a modified material, GLDA-LDH, which was subsequently applied for the adsorption of Pb(II) and Cd(II). Adsorption behavior was investigated through kinetic and isothermal models, with results indicating that the process followed pseudo-second-order kinetics and fit well with the Langmuir isotherm, suggesting chemisorption onto monolayer surface. The maximum adsorption capacities reached 219.2 mg/g for Pb(II) and 121.9 mg/g for Cd(II). Furthermore, GLDA-LDH exhibited a strong retention capability for metal ions with minimal desorption and remained effective in the presence of hard water and contaminated soils. XPS analysis revealed distinct interaction mechanisms; surface oxygen and carboxyl groups played a key role in Pb(II) adsorption, whereas nitrogen coordination was involved in Cd(II) uptake. These results point to the potential of GLDA-LDH as a reliable material for addressing heavy metal pollution and provide insights into the design of enhanced LDH-based adsorbents. Full article

Rare earth elements (Ln: Sm, Eu, Tb, Dy) were complexed with caffeic acid (Caf), a natural phenolic compound, to synthesize novel luminescent complexes with enhanced biological activities. The complexes, formulated as Ln(Caf)₃·4H₂O, were characterized using infrared spectroscopy (IR), thermogravimetric analysis (TGA/DTA), mass spectrometry (MS), and fluorescence spectroscopy. Structural studies confirmed the coordination of caffeic acid via carboxylate and hydroxyl groups, forming stable hexacoordinate complexes. Luminescence analysis revealed intense emission bands in the visible spectrum (480–700 nm), attributed to f-f transitions of Ln³⁺ ions, with decay lifetimes ranging from 0.054 to 0.064 ms. Biological assays demonstrated significant antibacterial activity against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa, with inhibition zones up to 44 mm at 200 µg/mL. The complexes also exhibited potent anticancer activity against MCF7 breast cancer cells, with Sm(Caf)₃·4H₃O showing the lowest IC₅₀ value (15.5 µM). This study highlights the dual functionality of rare earth metal-caffeic acid complexes as promising candidates for biomedical imaging and therapeutic applications. Full article

This study researches the impact of diclofenac (DCF) oxidation via UV/H₂O₂ on water quality, focusing on aromaticity and color changes. The process effectively degrades DCF and its intermediates through hydroxyl radical attack on the aromatic structure, leading to the formation of oxidized by-products. Initially, chromophoric compounds such as quinones and conjugated intermediates cause a yellow coloration, which diminishes as mineralization progresses. Turbidity remains below 1 NTU, aligning with European water quality standards. Aromaticity initially increases due to the stable intermediates (e.g., catechols and hydroquinones) but decreases as advanced oxidation cleaves aromatic rings. Kinetic modeling shows that DCF degradation follows first-order kinetics, while aromatic intermediates degrade via fractional-order kinetics (~0.3), indicating a non-linear relationship with concentration. The formation of chromophore compounds follows first-order kinetics, whereas their degradation transitions to zero-order kinetics when hydroxyl radicals are abundant. The study highlights the environmental relevance of these transformations, as aromatic intermediates like anilines and phenols, which contribute to water toxicity, are ultimately converted into less hazardous compounds (e.g., carboxylic acids and inorganic ions). Experimental validation confirms that degradation kinetics depend on hydrogen peroxide concentration, underscoring the potential of UV/H₂O₂ for water purification and pollutant removal. Full article

A chiral gelator (R)-H₆L with multiple carboxyl groups based on a 1,1′-bi-2,2′-naphthol (BINOL) skeleton was prepared, and it could form a supramolecular gel under the induction of water in DMSO/H₂O and DMF/H₂O (1/1, v/v). In the EtOH/H₂O system, the original partial gel transformed into a stable metal–organic gel (MOG), specifically with Cu²⁺ among 20 metal ions. It is proposed that Cu²⁺ coordinates with the carboxyl groups of (R)-H₆L to form a three-dimensional network structure. With the addition of a variety of α-hydroxy acids and amino acids, the Cu²⁺-MOG collapsed with merely 0.06 equivalents of L-tartaric acid (L-TA), while other acids required much larger amounts to achieve the same effect, realizing the visual chemoselective and enantioselective recognition of tartaric acid. Therefore, the chiral gelator (R)-H₆L achieved the tandem visual recognition of Cu²⁺ and chiral tartaric acid by sequence gel formation and collapse, offering valuable insights for visual sensing applications and serving as a promising model for future chiral sensor design. Full article