Search Results (332)

Tocopheramines are a class of antioxidants which are distinguished from tocopherols (vitamin E) by the presence of an amino group instead of the phenolic hydroxyl group. α-Tocopheramine is intensively studied for biomedical applications but also as a stabilizer for synthetic and natural polymers, in particular for cellulose solutions and spinning dopes for cellulosic fibers. This study addresses a fundamental difference in the oxidation chemistry of α-tocopheramine and its tocopherol counterpart: while the formation of the ortho-quinone methide (o-QM) involving C-5a is one of the most fundamental reactions of α-tocopherol, the corresponding ortho-iminoquinone methide (o-IQM) derived from α-tocopheramine has been elusive so far. Synthesis of the transient intermediate succeeded initially via 5a-hydroxy-α-tocopheramine, and its occurrence was confirmed by dimerization to the corresponding spiro-dimer and by trapping with ethyl vinyl ether. Eventually, suitable oxidation conditions were found which allowed for the generation of the o-IQM directly from α-tocopheramine. The underlying oxidation chemistry of α-tocopherol and α-tocopheramine is concisely discussed. Full article

This work presents the synthesis, characterization and evaluation of physicochemical and biological properties of two new aminoporphyrazine derivatives bearing magnesium(II) cations in their cores and peripheral pyrrolyl groups. The synthesis was carried out in several stages, using classical methods and the Microwave-Assisted Organic Synthesis (MAOS) approach. The obtained compounds were characterized using spectral techniques: UV-Vis spectrophotometry, mass spectrometry, ¹H and ¹³C NMR spectroscopy. The porphyrazine derivatives were tested for their electrochemical properties (CV and DPV), which revealed four redox processes, of which in compound 7 positive shifts of oxidation potentials were observed, resulting from the presence of free phenolic hydroxyl groups. In spectroelectrochemical measurements, changes in UV-Vis spectra associated with the formation of positive-charged states were noted. Photophysical studies revealed the presence of characteristic absorption Q and Soret bands, low fluorescence quantum yields and small Stokes shifts. The efficiency of singlet oxygen generation (Φ_Δ) was higher for compound 6 (up to 0.06), but compound 7, despite its lower efficiency (0.02), was distinguished by a better biological activity profile. Toxicity tests using the Aliivibrio fischeri bacteria indicated the lower toxicity of 7 compared to 6. The most promising result was the strong photodynamic activity of porphyrazine 7 against the Methicillin-resistant Stapylococcus aureus (MRSA) strain, leading to a more-than-5.6-log decrease in viable counts after the colony forming units (CFU) after light irradiation. Compound 6 did not show any significant antibacterial activity. The obtained data indicate that porphyrazine 7 is a promising candidate for applications in photodynamic therapy of bacterial infections. Full article

Resol phenol–formaldehyde (PF) resin was modified with 2.5 and 5.0 wt% polymethylhydrosiloxane (PMHS). This study characterizes the modified resin and its subsequently fabricated glass fiber (GF)-reinforced composites (30–60 wt% GF). Formation of an organic–inorganic hybrid network, via reaction between Si-H groups of PMHS and hydroxyl (-OH) groups of the resol resin, was confirmed by FTIR and ¹H NMR. DSC and TGA/DTG revealed enhanced thermal stability for PMHS-modified resin: the decomposition temperature of Resol–PMHS 5.0% increased to 483 °C (neat resin: 438 °C), and char yield at 800 °C rose to 57% (neat resin: 38%). The 60 wt% GF-reinforced Resol–PMHS 5.0% composite exhibited tensile, flexural, and impact strengths of 145 ± 7 MPa, 160 ± 7 MPa, and 71 ± 5 kJ/m², respectively, superior to the unmodified resin composite (136 ± 6 MPa, 112 ± 6 MPa, and 51 ± 5 kJ/m²). SEM observations indicated improved fiber–matrix interfacial adhesion and reduced delamination. These results demonstrate that PMHS modification effectively enhances the thermo-mechanical properties of the PF resin and its composites, highlighting potential for industrial applications. Full article

Bio-based polydithioacetal nanocomposites were synthesized to address the critical need for materials that simultaneously achieve enhanced thermomechanical properties and excellent reprocessing capabilities. Using vanillin and cellulose nanocrystals (CNCs) as starting materials, linear polydithioacetals (PDTAs) were prepared via acid-catalyzed polycondensation of vanillin with various dithiols including 1,6-hexanedithiol, 1,10-decanedithiol, 3,6-dioxa-1,8-octanedithiol and 2,2′-thiodiethanethiol. These PDTAs were then crosslinked with a diepoxide (i.e., diglycidyl ether of bisphenol A, DGEBA) via the reaction of phenolic hydroxyl groups of PDTAs with epoxide groups of DGEBA. To create the nanocomposites, cellulose nanocrystals (CNCs) were surface-functionalized with thiol groups and then incorporated as the reinforcing nanofillers of the networks. The results of morphological observation showed that the fine dispersion of CNCs in the polymer matrix was attained. Owing to the incorporation of CNCs, the nanocomposites displayed improved thermomechanical properties. Compared to the network without CNCs, the nanocomposite containing 20 wt% CNCs exhibited an increase of more than tenfold in modulus and threefold in tensile strength. In addition, the nanocomposites exhibited excellent reprocessing properties, attributable to the dynamic exchange of dithioacetal bonds. This work presents a promising strategy for developing bio-based nanocomposites that have not only improved thermomechanical properties but also excellent reprocessing (or recycling) properties. Full article

Infectious wounds pose formidable clinical challenges due to hypoxia, exacerbated inflammation, and persistent microbial colonization. To address this, we developed a bioinspired multifunctional hydrogel (PTDPs) through the in situ freeze-thaw co-assembly of polyvinyl alcohol (PVA), tea polyphenols (TP), polydopamine (PDA), and marine-derived self-assembling peptides (AAPs). The resultant PTDP hydrogel formed an intricate hydrogen-bonded network that enhanced mechanical robustness and substrate adhesion. TP and PDA synergistically confer potent antioxidant properties: TP scavenges radicals via phenolic hydroxyl groups while PDA enhances responsiveness to diverse radicals in hypoxic environments. Integrated with AAPs’ pro-regenerative functions and PDA’s broad-spectrum antimicrobial efficacy, this system generates therapeutic synergy. Characterization revealed outstanding physicochemical properties including tunable plasticity, high swelling ratios, and sustained hydration retention. In vitro studies demonstrated potent antioxidant activity, efficient inhibition of Staphylococcus aureus and Escherichia coli proliferation, and cytocompatibility facilitating endothelial cell migration/proliferation. In murine full-thickness infected wound models, the PTDP hydrogel significantly accelerated wound closure, enhanced neovascularization, and improved collagen deposition, underscoring its potential as an innovative therapeutic platform for infected and chronic wounds with strong translational prospects. Full article

Humic acid (HA), a major component of soil organic matter, is a naturally occurring macromolecule formed through the decomposition of plant and microbial residues. Its molecular structure comprises functional groups such as carboxyl, phenolic, hydroxyl, and carbonyl functional groups, which enable HA to interact with soil particles, nutrients, and biological systems. These interactions significantly contribute to soil fertility and overall plant productivity. Functionally, HA enhances soil health by increasing cation exchange capacity, improving water retention, and promoting the formation and stabilization of soil aggregates. In addition to its role in soil conditioning, HA is essential in mitigating plant stress. It achieves this by modulating antioxidant enzyme activity, stabilizing cellular membranes, and alleviating the adverse effects of abiotic stressors such as salinity, drought, and heavy metal toxicity. This review highlights the structural characteristics of HA, its structure-based functions, and the mechanisms involved in plant stress alleviation. Additionally, we explore how HA can be modified through physical, chemical, and biological approaches to enhance its agronomic performance. These modifications are designed to improve HA agronomic efficiency by increasing nutrient bioavailability, reducing environmental losses through minimized leaching and volatilization, and supporting sustainable agricultural practices. Overall, this review underscores the multifaceted roles of HA in promoting plant resilience to environmental stress, highlighting its potential as a key agent in the development of sustainable and eco-friendly crop production systems. Full article

Chitosan, a naturally occurring alkaline polysaccharide with excellent biocompatibility, non-toxicity, and renewability, has the ability to undergo cross-linking reactions with polyphenolic compounds. In this study, chitosan-encapsulated green tea extract microsphere resin (CS-GTEMR) was successfully prepared using chitosan and green tea extract via reversed-phase suspension cross-linking polymerization. The structural characterization of CS-GTEMR was conducted using Fourier Transform Infrared Spectroscopy (FTIR) and Differential Scanning Calorimetry (DSC). Additionally, its physical properties, swelling behavior, polyphenol content, and antioxidant activities were investigated. The results indicate that CS-GTEMR consists of reddish-brown microspheres with a smooth surface and dense pores. The study found that the total content of polyphenolic compounds encapsulated in CS-GTEMR was 50.485 ± 0.840 μg/g. The characteristic absorption peak of phenolic hydroxyl groups appeared in the FTIR spectrum, suggesting that the polyphenolic compounds had been successfully encapsulated within the CS-GTEMR. The equilibrium swelling ratio of CS-GTEMR was determined to be 229.7%, indicating their suitability for use in solutions with a pH range of 1–13. In simulated gastric and intestinal fluids, the release rates of polyphenolic compounds from CS-GTEMR were 24.934% and 3.375%, respectively, indicating that CS-GTEMR can exert a sustained-release effect on polyphenolic compounds. CS-GTEMR demonstrated antioxidant activities such as scavenging DPPH radicals, superoxide anion radicals, hydroxyl radicals, and hydrogen peroxide, as well as exhibiting iron-reducing and molybdenum-reducing powers. With its high mechanical strength, acid resistance, and organic solvent resistance, CS-GTEMR can protect polyphenolic compounds from damage. Therefore, CS-GTEMR can be utilized as a natural antioxidant or preventive agent in food, expanding the application scope of green tea extracts. Full article

Phenolic azobenzenes have garnered significant attention as functional materials due to their ability to undergo reversible photoisomerization and their potential for cation complexation. This review aims to provide a comprehensive overview of the recent developments in the synthesis, properties, and applications of phenolic azobenzene derivatives in cation binding and complexation. This article explores various synthetic strategies for the preparation of phenolic azobenzenes. Additionally, the mechanisms of cation complexation, including the role of the phenolic hydroxyl group and the azobenzene scaffold, are discussed, along with insights into the coordination chemistry involved. This review further examines the diverse applications of phenolic azobenzene complexes in fields such as ion sensing, catalysis, and biological and DSSC applications. Full article

This study aims to investigate the oxidative pyrolysis of biomass volatiles with a particular focus on the formation of liquid products. Furfural, hydroxyacetone, and 3,4-dimethoxybenzaldehyde were chosen as volatile model compounds. The impacts of the oxygen equivalence ratio (ER, 0–15%) and temperature (400–500 °C) on the product composition and distribution were examined using a two-stage quartz-tube reactor. The results showed that volatile pyrolysis was limited at the lower temperature of 400 °C even with oxygen introduction, while it could be significantly promoted at 500 °C as illustrated by the observed great decrease in the GC-MS peak areas of the volatile compounds especially under an oxidative atmosphere. For instance, the peak area of 3,4-dimethoxybenzaldehyde at 500 °C under an ER of 4% was only ~9% of that at 400 °C. Oxygen introduction enhanced the volatile decomposition with the formation of mainly permanent gases (although not given in the study) rather than liquid products, but distinct impacts were obtained for varied volatile compounds possibly due to their different chemical structures and autoignition temperatures. From the perspective of liquid product formation, furfural would undergo the cleavage of C-C/C-O bonds to form linear intermediates and subsequent aromatization to generate aromatics (benzene and benzofuran). The presence of oxygen could enhance the oxidative destruction of the C-C/C-O bonds and the removal of O from the molecules to form simple aromatics such as benzene, phenol, and toluene. Hydroxyacetone mainly underwent C-C/C-O cleavage that was further enhanced in the presence of oxygen; the resultant intermediates would recombine to generate acetoin and 2,3-pentanedione. A higher ER would directly oxidize the alcoholic hydroxyl group (-OH) into an aldehyde group (-CHO) to form methyl glyoxal, while 3,4-dimethoxybenzaldehyde mainly underwent cleavage and recombination of bonds connected with the benzene ring including aldehyde group (-CHO), C_Ar-O, C_Methoxy-O bonds, thus forming 1,2-dimethoxybenzene, toluene, and 3-hydroxybenzadehyde. This study provides more fundamental insights into the homogeneous oxidation of volatiles during the oxidative fast pyrolysis of biomass, facilitating the deployment of this technology. Full article

As one kind of renewable aromatic polymer, lignin is severely underused due to its chemical recalcitrance. Lignin can endure demethylation modification to improve its activation by releasing more active functional groups. However, the process suffers from expensive, corrosive, and toxic issues by employing halogen-containing reagents, which has become an obstacle to industrial applications. Herein, a series of dicarboxylic acid-based protic ionic liquids (DAPILs) systems composed of ethanolamine and dibasic organic acids (e.g., aspartic acid (Asp), glutamic acid (Glu), succinic acid (SA), and glutaric acid (GA)) with 1~2:1 stoichiometric ratio, have been finely designed for the demethylation of industrial lignin. With [EOA][GA] treatment, the polyphenol content in lignin was favorably increased beyond 1.58 times. The structural tailoring and variation were fully characterized by 2D HSQC and ¹H NMR. The analysis results indicated that, with the increase of phenolic hydroxyl content in lignin, the β-O-4′ bond was broken and the content of structural units (S, G) and the S/G ratio of lignin decreased accordingly. After the treatment, the used IL and tailored lignin can be recovered over 95%. This novel, halogen-free and environmentally friendly lignin-cutting strategy not only opens avenues for high-value utilization of lignin but also expands the field of application of dicarboxylic acid-based protic ionic liquids. Full article

Radix astragali is a homologous plant of medicine and food with a variety of health benefits. However, our previous study showed that blue mold, caused by Penicillium polonicum, is the most important postharvest disease of fresh R. astragali during storage. Ozone, as a strong oxidizing agent, can effectively control the occurrence of postharvest diseases in fruits and vegetables. Nevertheless, there are few research studies on the effect of ozone-treated fresh Chinese traditional medicine. In this study, we investigated the effect of ozone gas on the postharvest blue mold development, mycotoxin accumulation, and main active component contents in fresh R. astragali infected by P. polonicum, and analyzed the possible action mechanism on ROS metabolism. The result indicates that ozone application significantly inhibited the development of postharvest blue mold caused by P. polonicum infection, reduced the disease incidence, disease index, and weight loss rate, maintained the main active ingredients in fresh R. astragali by activating ROS metabolism, enhanced the antioxidant enzymatic activity, thus avoiding oxidative damage caused by excessive ROS accumulation, and maintained the integrity of the cell membrane, ultimately controlling the occurrence of blue mold of R. astragali. Moreover, ozone treatment also maintained the contents of the main active ingredients in R. astragali before 14 d during P. polonicum infection. In addition, the amount of active ingredients of astragaloside I, calycosin-7-glucoside, and ononin in the ozone-treated group was higher than that in the control group during the storage period. We speculate that, under the action of ozone, astragaloside IV was converted into astragaloside II by oxidative modification and astragaloside II was further oxidized to astragaloside I, resulting in the accumulation of astragaloside I. Similarity, the hydrogen atoms (-H) on the benzene ring in formononetin were oxidized to phenolic hydroxyl groups (-OH) to generate calycosin, which was further converted into calycosin-7-glucoside, resulting in calycosin-7-glucoside accumulation. This study will provide the theoretical basis for ozone commercial application to control the occurrence of postharvest diseases of R. astragali. Full article

The structural complexity and variability of dissolved organic matter (DOM) significantly affect its binding capacity with heavy metals (HMs). This study evaluated the remediation efficacy of biochar (BC) and humic acid (HA) on Mn- and Cu-contaminated soils using four maize pot treatments: 3% BC (YB3), 6% BC (YB6), 3% BC + 1% HA (YB3H), and 6% BC + 1% HA (YB6H). The results showed that compared to the control (Y), Results showed Mn and Cu concentrations in rhizosphere soil decreased by 11.08–17.76%, while DOM content increased by 44.2–103.83%. BC enhanced DOM aromaticity and humification, further intensified by HA, leading to a more complex and stable DOM structure. PARAFAC identified four DOM components in BC (BC-DOM): C1 (fulvic-like), C2/C3 (humic-like), and C4 (protein-like), and in BC + HA (BC + H-DOM), an enhanced structural complexity with additional aromatic C–H groups was observed. 2D-COS analysis revealed that in BC-DOM, polysaccharides primarily interacted with Mn and Cu, followed by carboxylic acids and phenolic hydroxyl groups, but in BC + H-DOM, aromatic C–H groups preferentially bound Cu before polysaccharides, showing weaker affinity for Mn. These results elucidate the DOM-mediated immobilization mechanisms of BC and HA for HMs, offering insights for soil remediation and carbon sequestration strategies. 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

Catalytic hydrogenolysis of lignin to produce high-value monophenols has emerged as a pivotal strategy in modern biorefineries. In this study, we synthesized spherical nitrogen-doped porous carbon (SNCB) materials by using Al/Co-BTC as a precursor, introducing melamine as a supplementary carbon and nitrogen source, and activating the material with NaOH solution. The SNCB framework was decorated with Cu-Pd bimetallic nanoparticles, exhibiting outstanding catalytic activity in the hydrogenolytic depolymerization of organosolv lignin. The Cu-Pd@SNCB catalyst exhibited remarkable activity, attributed to the hierarchical porous structure of SNCB that facilitated metal nanoparticle dispersion and reactant accessibility. The synergistic effect between Cu as the reactive site for reactant adsorption and Pd as the reactive site for H₂ adsorption enhanced the catalytic activity of the catalyst. Systematically optimized conditions (2 MPa H₂, 270 °C, 3 h) yielded 43.02 wt% phenolic monomers, with 4-(3-hydroxypropyl)-2,6-dimethoxyphenol dominating the product profile at 46.3% selectivity. The catalyst and its reaction products were analyzed using advanced characterization techniques, including XPS, XRD, TEM, SEM, BET, GC-MS, GPC, 2D HSQC NMR, and FT-IR, to elucidate the reaction mechanism. The mechanism proceeds through: (1) nucleophilic substitution of the β-O-4 hydroxyl group by MeOH, followed by (2) simultaneous hydrogenolytic cleavage of C_β-O and C_α-O bonds mediated by Cu-Pd@SNCB under H₂ atmosphere, which selectively produces 4-(3-hydroxypropyl)-2,6-dimethoxyphenol and 4-propyl-2,6-dimethoxyphenol. This study proposes a bimetallic synergistic mechanism, offering a general blueprint for developing selective lignin valorization catalysts. Full article

Triboelectric nanogenerators (TENGs) are ideal for meeting the global demand for sustainable energy in energy harvesting and wearable electronics. While biomaterials like polysaccharides are well studied in TENGs, the potential of polyphenols and the role of phenolic groups in contact electrification remain underexplored. This study bridges the gap by using tannic acid (TA) to rapidly prepare TA-Fe³⁺ complex-coated particle films in 1.2 min. Analysis reveals that phenolic hydroxyl groups are strong electron donors, with Fe³⁺ enhancing electron affinity by restricting their mobility and lowering molecular orbital energy levels. Adjusting the pH to control complex states enables the regulation of triboelectric charging behavior between positive and negative. Investigations into film micromorphology and particle size further optimize performance, with the tris-complex exhibiting negative charging behavior achieving exceptional stability and a high charge density of 92.5 μC·m⁻². Additionally, integrating biomaterials into bio-TENGs and exploring the film’s pH and ion sensitivity broaden its applications, demonstrating versatile properties. This study clarifies the triboelectric properties of phenolic groups and proposes methods to regulate charging behavior, offering novel insights for developing biomaterials in TENGs. Full article