Radical Scavenging Mechanism Research Articles

Effect of Quantity of Plant Extract on Physicochemical Properties and Biomedical Applications of Phytoconstituent-Coated ZnONPs

This study delved into how the quantity of extract (Withania somnifera root) affects the physicochemical properties and biomedical applications of ZnONPs. For this study, three samples of phytoconstituents-coated ZnONPs were prepared by altering the extract volume i.e., 10[Formula: see text]mL, 20[Formula: see text]mL and 30[Formula: see text]mL of 10% (w/v) extract solution (corresponding samples were marked as WS10, WS20 and WS30). UV–Vis spectroscopy preliminary confirms the formation of ZnONPs with surface plasmon resonance (SPR) peaks at 361[Formula: see text]nm, 359[Formula: see text]nm and 356[Formula: see text]nm for WS10, WS20 and WS30 samples, respectively. Fourier transform infrared data confirmed the presence of different functional groups. X-ray diffraction revealed the crystalline nature and high purity of samples. FESEM confirmed spherical-shaped ZnONPs with an average particle size of 72–88 nm. The agar well diffusion assay results indicated that out of three samples, WS30 has maximum antibacterial activity, with inhibition zones of [Formula: see text][Formula: see text]mm (against Escherichia coli) and [Formula: see text][Formula: see text]mm (against Streptococcus mutans). Synthesized samples also exhibited mild antioxidant activity. Additionally, we proposed a radical scavenging mechanism for phytoconstituents-coated ZnONPs. The MTT assay suggests WS30 exhibited excellent anticancer activity with IC[Formula: see text] of [Formula: see text] against human liver cancer cells (HepG2), while comparatively lower toxicity was observed against normal human melanoma cells (HaCaT) with IC[Formula: see text] of [Formula: see text]. This work is novel as it investigates the effects of phytoconstituents amount on the production of ZnONPs as reducing and coating agents that play a critical role in their overall biomedical applications.

Transformation mechanism, kinetics and ecotoxicity of kaempferol and quercetin in the gaseous and aqueous phases: A theoretical combined experimental study.

The transformation and risk assessment of flavonoids triggered by free radicals deserve extensive attention. In this work, the degradation mechanisms, kinetics, and ecotoxicity of kaempferol and quercetin mediated by ∙OH, ∙OCH3, ∙OOH, and 1O2 in gaseous and aqueous environments were investigated using cell experiments and quantum chemical calculations. Three radical scavenging mechanisms, including hydrogen atom transfer (HAT), radical adduct formation (RAF) and single electron transfer (SET) were discussed. The results show that RAF and HAT are the main reaction mechanisms for the neutral kaempferol/quercetin, and SET mechanism is important for the anionic kaempferol/quercetin. The overall rate coefficient of kaempferol and quercetin with ∙OH were calculated at 273-323K, and the aqueous rate coefficients are calculated by considering the rates of neutral and monoanionic forms multiplied with the molar fractions of each form. The values are 2.81×1010 and 8.63×1010M-1s-1 in the aqueous environment, and 2.31×10-10 and 1.18×10-10cm3 molecule-1s-1 in the gaseous environment at 298K. Fluorescence probe and flow cytometry results show that kaempferol and quercetin can be efficiently degraded by free radicals, and quercetin has a better effect, which is consistent with the theoretical results in the aqueous environment. The transformation mechanism of Q-OH-P7a with ∙OH, O2 and NO was studied, and the stable product is Q-P1. Toxicology results show that most of the subsequent products of quercetin do not bioaccumulate and can be biodegraded, but most products still have toxic properties or harmful properties and show positive mutagenicity. This study provides new guidance for flavonoid degradation behavior and environmental risks.

Synthesis of nitrogen and phosphorus-doped chitosan derivatives for enhanced flame retardancy, smoke suppression, and mechanical properties in epoxy resin composites.

Biomass-based flame retardants have attracted significant academic interest due to their environmental benefits and sustainability. Nevertheless, devising straightforward, eco-friendly, and mild methodologies to synthesize flame retardants of epoxy resins (EP) remains a formidable challenge. This paper reports the successful synthesis of a novel nitrogen and phosphorus-doped chitosan derivatives flame retardant (MMCA) utilizing phytic acid, chitosan, and melamine cyanurate via electrostatic self-assembly and physical encapsulation in an acidic aqueous solution. The incorporation of 5wt% MMCA into the EP readily achieved a UL-94V-0 rating. This improvement can be primarily attributed to the early formation of a continuous, dense, robust, and expanded char layer during combustion, coupled with the synergistic flame retardant mechanisms of radical scavenging and the dilution of non-combustible gases. Compared to pristine EP, EP/5MMCA exhibited significant reductions of 23.7%, 29.2%, and 24% in total smoke production rate, peak heat release rate, and peak smoke production rate, respectively. Moreover, the strategic introduction of MMCA also enhanced the glass transition temperature, storage modulus, and crosslinking density of EP, improving its tensile, compressive and impact properties. This study proposes a simple, viable, and environmentally sustainable strategy for the fabrication of biomass-based flame retardants, resulting in notable improvements the flame retardancy, smoke suppression, fire safety, and mechanical robustness of EP.

A DFT analysis of the antioxidant capacity of scopolin and scopoletin.

Scopolin and scopoletin belong to the class of coumarins and have experimentally proven natural antioxidants. Natural antioxidants are crucial in mitigating the impact of oxidants in the human body through radical scavenging. Even though scopolin and scopoletin are proven antioxidants by experimental results, their antioxidant mechanisms still remained unexplained. In this study, Density functional theory (DFT) calculations were used to study the radical scavenging mechanisms of both scopolin and scopoletin using kinetic and thermodynamics parameters. The global parameters indicated that both scopolin and scopoletin have antioxidant properties. The band gap energy revealed that scopoletin (4.18eV) has strong antioxidant activity compared to scopolin (4.31eV). These studies found that hydrogen atom transfer (HAT) is the primary mechanism for CH3OO• radical scavenging at the C-H bond in scopolin (91.98kcal.mol-1) and the O-H bond in scopoletin (77.05kcal.mol-1) due to their lowest bond dissociation energies. The calculated activation energy ( ) for the radical scavenging reaction, reconfirmed scopoletin ( =11.19kcal.mol-1) performed as a better antioxidant compared to scopolin ( =20.91kcal.mol-1). In this study, the results of DFT calculations confirmed that scopoletin exhibits a higher antioxidant capacity, and HAT mechanism is the most effective radical scavenging mechanism. The antioxidant activity of scopolin and scopoletin was determined by DFT at the B3LYP/6-31G(d) level of theory. Global parameter calculations and frontier molecular orbital analysis were conducted to assess these compounds' capacity for scavenging radicals. Hydrogen atom transfer (HAT), sequential electron transfer proton transfer (SETPT), and sequential proton loss electron transfer (SPLET) mechanisms were the three main mechanisms that were taken into consideration. The potential energy surface (PES) verified the most appropriate processes shown by the enthalpy calculations.

Catechol-derived Mannich bases: radical regulatory properties, cytotoxicity and interaction with biomolecules

Free radicals are ubiquitous in biological systems, being responsible for pathogenesis of degenerative diseases and participating in vitally important biochemical processes, which are mediated by radical regulatory agents. The effects of the aliphatic amine substituents in the catechol-derived Mannich bases on their antioxidant and pro-oxidant activity were investigated. It has been found that the presence of catechol moiety in the structure of Mannich bases allows them to act as Cu(II) reductants, efficient Fe(II) chelators and potent DPPH radical scavengers. It has been found that the plausible mechanism of the DPPH radical scavenging proceeds via quinone formation, followed by their interaction with ethanol via the Michael addition reaction. In the neutrophil respiratory burst assay, several compounds have demonstrated a weak antioxidant activity at the micromolar level (0.1–10 µM), whereas at the millimolar level (0.1 mМ) a strong pro-oxidant effect has been observed. Additionally, at the highest used concentrations a pronounced cytotoxicity against dermal fibroblasts DF-2 and an immunosuppressive effect against T-lymphocytes have been observed for all the synthesized compounds. It has been demonstrated that the oxidation of catechols in the presence of low-molecular thiols results in the formation of covalent adducts, which provides an insight into their cytotoxicity and detoxification pathways.

Exploring the relationship between lignin structure and antioxidant property using lignin model compounds

Lignin has a natural polyphenol structure that is expected to replace chemically synthesized antioxidants as a native antioxidant with biodegradable and convenient source characteristics. However, the improvement of the antioxidant property of lignin and its application as an antioxidant are still somewhat limited due to the lack of understanding of the relationship between specific lignin structures and antioxidant property. Therefore, the study of the relationship between lignin structure and antioxidant property is crucial to realize the high-quality application of lignin. In this experiment, the scavenging ability of free 1,1-diphenyl-2-picrylhydrazyl (DPPH·) radicals was determined for different grades of acetylated tannins, typical lignin model compounds and different structural units of milled wood lignin to investigate the relationship between lignin structure and antioxidant property. Based on the experimental results, some structure-activity relationships were proposed and the mechanism of the antioxidant property of lignin was discussed. The number of phenolic hydroxyl groups was linearly and positively correlated with antioxidant property, and the scavenging of DPPH radicals increased significantly with the increase in the number of methoxy groups in the model compounds. Moreover, aldehyde and carboxyl groups had a negative effect on the antioxidant property of lignin, while methoxy, alkyl and alcohol hydroxyl groups played a positive role. The guaiacyl (G) and syringyl (S) units favored the antioxidant property, so the difference in the content of structural units in lignin under certain conditions of phenolic hydroxyl content also affected the antioxidant property. Therefore, the antioxidant property of aspen milled lignin was higher than that of other milled lignin from different wood species. Finally, the mechanism of DPPH free radical scavenging by lignin was revealed to better understand the relationship between lignin structure and antioxidant property.

Correction to: Radical scavenging mechanism of aryl carbamate: a computational case study using 3-morpholinopropyl phenyl carbamate

Correction to: Radical scavenging mechanism of aryl carbamate: a computational case study using 3-morpholinopropyl phenyl carbamate

Computational Insights into the Radical Scavenging Activity and Xanthine Oxidase Inhibition of the Five Anthocyanins Derived from Grape Skin.

Anthocyanins, typical polyphenol compounds in grape skin, have attracted increasing interest due to their health-promoting properties. In this body of work, five representative anthocyanins (Cy-3-O-glc, Dp-3-O-glc, Pn-3-O-glc, Mv-3-O-glc, and Pt-3-O-glc) were studied using the density functional theory (DFT) to elucidate structure-radical scavenging activity in the relationship and the reaction path underlying the radical-trapping process. Based on thermodynamic parameters involved in HAT, SET-PT, and SPLET mechanisms, along with the structural attributes, it was found that the C4' hydroxyl group mainly contributes to the radical scavenging activities of the investigated compounds. Pt-3-O-glc exhibits a good antioxidant capacity among the five compounds. The preferred radical scavenging mechanisms vary in different phases. For the Pt-3-O-glc compound, the calculations indicate the thermodynamically favoured product is benzodioxole, rather than o-quinone, displaying considerably reduced energy in double HAT mechanisms. Additionally, the thermodynamic and kinetic calculations indicate that the reaction of •OH into the 4'-OH site of Pt-3-O-glc has a lower energy barrier (7.6 kcal/mol), a higher rate constant (5.72 × 109 M-1 s-1), and exhibits potent •OH radical scavenging properties. Molecular docking results have shown the strong affinity of the studied anthocyanins with the pro-oxidant enzyme xanthine oxidase, displaying their significant role in inhibiting ROS formation.

DFT-based computational analysis of 2,4-dimethyl-6-tert-butylphenol (DTBP) as an antioxidant in aviation fuels

Antioxidants are indispensable additives for ensuring the long-term stability, performance, and reliability of aviation fuels. They prevent the formation of gum and other insoluble deposits in the fuel which clog fuel systems, leading to engine problems. This is achieved by inhibiting free radical chain reactions involved in the oxidation of hydrocarbons in the fuel. The compound 2,4-Dimethyl-6-tert-butyl phenol (DTBP) is one of the widely used antioxidants in aviation fuels. In this report, the radical scavenging done by DTBP is analysed computationally by density functional theory (DFT) with the model chemistry X/6-31+G(d,p), where X represents certain Minnesota functionals such as MN15, M05-2X, M06-2X, M08-HX, and M11. Among the well-known modes of radical scavenging, namely HAT, SETPT, and SPLET, the HAT mode is preferred in the gaseous phase, while SPLET operates in non-polar solvents, as computations indicate. Fukui indices, global reactivity descriptors, electronic spectra, and natural bond orbitals (NBOs) are also generated to explain the results. Understanding the mechanism of radical scavenging is important in designing powerful and efficient antioxidants for aviation fuels such as jet fuel, aviation gasoline, Jet B, and bio-kerosene.

Interactions between lipid oxidation and anthocyanins from black carrots in ω-3 fatty acid-rich flaxseed oil-in-water emulsions

The application of anthocyanins as red colorants in lipid-containing foods such as oil-in-water emulsions is challenging due to their ability to act as antioxidants and their instability under various environmental conditions. In this study, we investigated the kinetics of black carrot anthocyanin degradation and the subsequent color loss influenced by lipid oxidation reactions in 1% (w/w) flaxseed oil-in-water emulsions stabilized by 0.1% (w/w) sodium dodecyl sulfate (SDS) at pH 2 upon storage at 35 °C for ten days under light and in the dark. Oxidatively stable Miglyol oil-in-water emulsions and SDS solutions were used as reference. The results showed simultaneous formation of lipid hydroperoxides and degradation of anthocyanins. The addition of anthocyanins decreased lipid hydroperoxide formation, confirming the antioxidant activity of anthocyanins through radical scavenging mechanism. The kinetic modelling of lipid oxidation and anthocyanin degradation are particularly important for estimating color stability in colored emulsion-based food systems such as dairy or non-dairy milk or yoghurt drinks.Graphical abstract

Unlocking the potential of Allium dictyoprasum C.A. Meyer ex Kunth: quantum chemical insights into radical scavenging, chemical composition, phenolic content, and antimicrobial activity

ABSTRACT Allium dictyoprasum C.A. Meyer ex Kunth (A. dictyoprasum) underwent comprehensive analysis, encompassing quantum chemical computations to assess its radical scavenging potential, chemical and elemental composition, total phenolic content, and antimicrobial activity. Experimental and theoretical investigations focused on elucidating the radical scavenging properties of polyhydroxy phenolic compounds present in the plant. Quantum chemical calculations were employed to evaluate the antioxidants employed to evaluate selected polyhydroxy phenolic molecules including flavonoids, hydrocinnamic acid derivatives, and hydroxybenzoic acid derivatives from natural sources. Thermochemical parameters of these compounds were calculated by the B3LYP/6–311 G++(d,p) level in both gas and solvent phases to elucidate the radical scavenging mechanism including hydrogen atom transfer (HAT), single electron transfer followed by proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET). Analysis of A. dictyoprasum extracts obtained via various extraction methods revealed the presence of several major compounds, including dimethyl trisulfide, 3,5-Dihydroxy-6-methyl-2,3-dihydro-4 H-pyran-4-one, 2-Methoxy-4-vinylphenol, Dimethyl phthalate, Methyl palmitate, Methyl oleate, Methyl stearate, (9Z)-9-Octadecenamide. Notably, Malic acid and Quinic acid were identified as major compounds, with concentrations of 43.31 and 17.47 mg kg−1 extract, respectively, based on LC-MS/MS analysis. The total phenolic content of the extract was measured as 17.83 mg gallic acid/mL, while its free radical scavenging activity was 80.89% per mg/mL. Elemental analysis revealed significant levels of Mg, K, Na, Fe, and P, with minor concentrations of elements such as Ti, Tl, B, and Be. Furthermore, A. dictyoprasum exhibited notable antibacterial activity against various bacteria strains, surpassing the efficacy of some commercial antibiotics.

Exploring the Neuroprotective Potential of Desmodium Species: Insights into Radical Scavenging Capacity and Mechanisms against 6-OHDA-Induced Neurotoxicity.

In this study, we collected seven prevalent Taiwanese Desmodium plants, including three species with synonymous characteristics, in order to assess their antioxidant phytoconstituents and radical scavenging capacities. Additionally, we compared their inhibitory activities on monoamine oxidase (MAO) and 6-hydroxydopamine (6-OHDA) auto-oxidation. Subsequently, we evaluated the neuroprotective potential of D. pulchellum on 6-OHDA-induced nerve damage in SH-SY5Y cells and delved into the underlying neuroprotective mechanisms. Among the seven Desmodium species, D. pulchellum exhibited the most robust ABTS radical scavenging capacity and relative reducing power; correspondingly, it had the highest total phenolic and phenylpropanoid contents. Meanwhile, D. motorium showcased the best hydrogen peroxide scavenging capacity and, notably, D. sequax demonstrated remarkable prowess in DPPH radical and superoxide scavenging capacity, along with selective inhibitory activity against MAO-B. Of the aforementioned species, D. pulchellum emerged as the frontrunner in inhibiting 6-OHDA auto-oxidation and conferring neuroprotection against 6-OHDA-induced neuronal damage in the SH-SY5Y cells. Furthermore, D. pulchellum effectively mitigated the increase in intracellular ROS and MDA levels through restoring the activities of the intracellular antioxidant defense system. Therefore, we suggest that D. pulchellum possesses neuroprotective effects against 6-OHDA-induced neurotoxicity due to the radical scavenging capacity of its antioxidant phytoconstituents and its ability to restore intracellular antioxidant activities.

Radical scavenging mechanism of aryl carbamate: a computational case study using 3-morpholinopropyl phenyl carbamate

Radical scavenging mechanism of aryl carbamate: a computational case study using 3-morpholinopropyl phenyl carbamate

Unravelling the Influence of Chlorogenic Acid on the Antioxidant Phytochemistry of Avocado (Persea americana Mill.) Fruit Peel.

Oxidative stress is pivotal in the pathology of many diseases. This study investigated the antioxidant phytochemistry of avocado (Persea americana Mill.) peel. Different solvent extracts (dichloromethane, ethyl acetate, methanol, and water) of avocado peel were subjected to total phenol and flavonoid quantification, as well as in vitro radical scavenging and ferric reducing evaluation. The methanol extract was subjected to gradient column chromatographic fractionation. Fraction 8 (eluted with hexane:chloroform:methanol volume ratio of 3:6.5:0.5, respectively) was subjected to LC-MS analysis. It was assessed for cellular inhibition of lipid peroxidation and lipopolysaccharide (LPS)-induced ROS and NO production. The DPPH radical scavenging mechanism of chlorogenic acid was investigated using Density Functional Theory (DFT). The methanol extract and fraction 8 had the highest phenol content and radical scavenging activity. Chlorogenic acid (103.5 mg/mL) and 1-O-caffeoylquinic acid (102.3 mg/mL) were the most abundant phenolics in the fraction. Fraction 8 and chlorogenic acid dose-dependently inhibited in vitro (IC50 = 5.73 and 6.17 µg/mL) and cellular (IC50 = 15.9 and 9.34 µg/mL) FeSO4-induced lipid peroxidation, as well as LPS-induced ROS (IC50 = 39.6 and 28.2 µg/mL) and NO (IC50 = 63.5 and 107 µg/mL) production, while modulating antioxidant enzyme activity. The fraction and chlorogenic acid were not cytotoxic. DFT analysis suggest that an electron transfer, followed by proton transfer at carbons 3'OH and 4'OH positions may be the radical scavenging mechanism of chlorogenic acid. Considering this study is bioassay-guided, it is logical to conclude that chlorogenic acid strongly influences the antioxidant capacity of avocado fruit peel.

A self-cascade terpolymer platform for amplified chemo-chemodynamic therapy with synergistic immunogenic cell death enhancement

A self-cascade terpolymer platform for amplified chemo-chemodynamic therapy with synergistic immunogenic cell death enhancement

Redox-Mediated Amination of Pyrogallol-Based Polyphenols.

Flavonoids are known to covalently modify amyloidogenic peptides by amination reactions. The underlying coupling process between polyphenols and N-nucleophiles is assessed by several in vitro and in silico approaches. The coupling reaction involves a sequence of oxidative dearomatization, amination, and reductive amination (ODARA) reaction steps. The C6-regioselectivity of the product is confirmed by crystallographic analysis. Under aqueous conditions, the reaction of baicalein with lysine derivatives yields C-N coupling as well as hydrolysis products of transient imine intermediates. The observed C-N coupling reactions work best for flavonoids combining a pyrogallol substructure with an electron-withdrawing group attached to the C4a-position. Thermodynamic properties such as bond dissociation energies also highlight the key role of pyrogallol units for the antioxidant ability. Combining the computed electronic properties and in vitro antioxidant assays suggests that the studied pyrogallol-containing flavonoids act by various radical-scavenging mechanisms working in synergy. Multivariate analysis indicates that a small number of descriptors for transient intermediates of the ODARA process generates a model with excellent performance (r=0.93) for the prediction of cross-coupling yields. The same model has been employed to predict novel antioxidant flavonoid-based molecules as potential covalent inhibitors, opening a new avenue to the design of therapeutically relevant anti-amyloid compounds.

Theoretical exploration of the antioxidant activity of honokiol and magnolol

Theoretical exploration of the antioxidant activity of honokiol and magnolol

Radical Scavenging Mechanism and Antioxidant Effect of Fullerenes in Lubricating Oils (Part 3)

Radical Scavenging Mechanism and Antioxidant Effect of Fullerenes in Lubricating Oils (Part 3)

Investigation of novel radical scavenging mechanisms in the alkaline environment: Green, sustainable and environmentally friendly antioxidative agent(s)

Pharmaceutical and industrial utilization of synthetic chemicals has an immerse impact on the environment. In that sense, novel chemicals with potential for industrial application should be investigated for their behaviour in reactions with hydroxyl radical, simulating AOPs (Advanced Oxidation Processes). AOPs are known for being highly effective in wastewater management and natural water remediation. In this paper, exhaustive research on the radical scavenging activity of a newly synthesized coumarin derivative (4HCBH), as a representative of the series of coumarin-benzohydrazides with high antioxidative potential was conducted. This study took into consideration the pH value range significant for practically all living organisms (pH=7.0-8.5). According to the experimentally obtained results, the 4HCBH showed an increase in radical scavenging activity, following the slight increase in pH values, which suggested that the formation of anionic form of 4HCBH is responsible for its antiradical activity. Further investigations led to the postulation of a novel mechanistic approach called Sequential Proton Loss Electron Transfer - Radical-Radical Coupling (SPLET-RRC), in which, by a series of steps, a new, stable compound was formed. Furthermore, it was demonstrated that the product generated through SPLET-RRC showed lower toxicity than the parent molecule.

A DFT-Based Mechanism Analysis of the Cyclodextrin Inclusion on the Radical Scavenging Activity of Apigenin.

Natural flavonoids are renowned for their exceptional antioxidant properties, but their limited water solubility hampers their bioavailability. One approach to enhancing their water solubility and antioxidant activity involves the use of cyclodextrin (CD) inclusion. This study investigated the impact of CD inclusion on the three primary radical scavenging mechanisms associated with flavonoid antioxidant activity, utilizing apigenin as a representative flavonoid and employing density functional theory (DFT) calculations. Initially, the optimized geometries of CD-apigenin inclusion complexes were analyzed, revealing the formation of hydrogen bonds between CD and apigenin. In less polar environments, the inclusion complex strengthened the bond dissociation enthalpies of hydroxyl groups, thereby reducing antioxidant activity. Conversely, in polar environments, the inclusion complex had the opposite effect by lowering proton affinity. These findings align with experimental results demonstrating that CD inclusion complexation enhances flavonoid antioxidant activity in aqueous ethanol solutions.