Radical Cation Research Articles

Tailoring the Degradation of Cyanoarene‐Based Photocatalysts for Enhanced Visible‐Light‐Driven Halogen Atom Transfer

AbstractWe present the strategic design of donor‐acceptor cyanoarene‐based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)‐induced dehalogenation reactions. Our investigation reveals a competitive nature between the catalytic cycle and the degradation pathway, with the degradation becoming dominant, particularly for less activated alkyl halides. The degradation behavior of PCs significantly impacts the efficiency of the XAT process, leading to exploration into manipulating the degradation behavior in a desirable direction. Recognizing the variation in the nature and rate of PC degradation, as well as its influence on the reaction across the range of PC structures, we carefully engineered the PCs to develop a pre‐catalyst, named 3DP‐DCDP‐IPN. This pre‐catalyst undergoes rapid degradation into an active form, 3DP‐DCDP‐Me‐BN, exhibited an enhanced reducing ability in its radical anion form to induce better PC regeneration and consequently effectively catalyzes the XAT reaction, even with a challenging substrate.

Chromium Complexes with Benzanellated N‐Heterocyclic Phosphenium Ligands–Synthesis, Reactivity and Application in Catalytic CO2 Reduction

AbstractA chromium complex carrying two benzanellated N‐heterocyclic phosphenium (bzNHP) ligands was prepared by a salt metathesis approach. Spectroscopic studies suggest that the anellation enhances the π‐acceptor ability of the NHP‐units, which is confirmed by the facile electrochemical reduction of the complex to a spectroscopically characterized radical anion. Co‐photolysis with H2 allowed extensive conversion into a σ‐H2‐complex, which shows a diverse reactivity towards donors and isomerizes under H−H bond fission and shift of a hydride to a P‐ligand. The product carrying phosphenium, phosphine and hydride ligands was also synthesized independently and reacts reversibly with CO and MeCN to yield bis‐phosphine complexes under concomitant Cr‐to‐P‐shift of a hydride. In contrast, CO2 was not only bound but reduced to give an isolable formato complex, which reacted with ammonia borane under partial recovery of the metal hydride and production of formate. Further elaboration of the reactions of the chromium complexes with CO2 and NH3BH3 allowed to demonstrate the feasibility of a Cr‐catalyzed transfer hydrogenation of CO2 to methanol. The various complexes described were characterized spectroscopically and in several cases by XRD studies. Further insights in reactivity patterns were provided through (spectro)electrochemical studies and DFT calculations.

Stable Meisenheimer Complexes as Powerful Photoreductants Readily Obtained from Aza‐Heteroaromatic Compounds

Excited states of radical anions derived from the photoreduction of stable organic molecules are suggested to serve as potent reductants. However, excited states of these species are too short‐lived to allow bimolecular quenching processes. Recently, the singlet excited state of Meisenheimer complexes, which possess a long‐lived excited state, was identified as the competent species for the reduction of challenging organic substrates (–2.63 V vs. SCE, saturated calomel electrode). To produce reasonably stable and simply accessible different Meisenheimer complexes, the addition of nBuLi to readily available aromatic heterocycles was investigated, and the photoreactivity of the generated species was studied. In this paper, we present the straightforward preparation of a family of powerful photoreductants (*Eox<–3 V vs. SCE in their excited states, determined by DFT and time‐dependent TD‐DFT calculations; (DFT, density functional theory) that can induce dehalogenation of electron‐rich aryl chlorides and to form C−C bond through radical cyclization. Photophysical analyses and computational studies in combination with experimental mechanistic investigations demonstrate the ability of the adduct to act as a strong electron donor under visible light irradiation.

Tailoring the Degradation of Cyanoarene-Based Photocatalysts for Enhanced Visible-Light-Driven Halogen Atom Transfer.

We present the strategic design of donor-acceptor cyanoarene-based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)-induced dehalogenation reactions. Our investigation reveals a competitive nature between the catalytic cycle and the degradation pathway, with the degradation becoming dominant, particularly for less activated alkyl halides. The degradation behavior of PCs significantly impacts the efficiency of the XAT process, leading to exploration into manipulating the degradation behavior in a desirable direction. Recognizing the variation in the nature and rate of PC degradation, as well as its influence on the reaction across the range of PC structures, we carefully engineered the PCs to develop a pre-catalyst, named 3DP-DCDP-IPN. This pre-catalyst undergoes rapid degradation into an active form, 3DP-DCDP-Me-BN, exhibited an enhanced reducing ability in its radical anion form to induce better PC regeneration and consequently effectively catalyzes the XAT reaction, even with a challenging substrate.

Nanofibrous La0.95K0.05MnO3 perovskite with improved photoelectrical properties for photocatalytic degradation of antibiotics

Potassium doped lanthanum manganese perovskite oxides, La1−xKxMnO3, with nanofibrous structure, are prepared and used for Photo-Fenton degradation of antibiotics, including ciprofloxacin (CIP), tetracycline (TC), and sulfathiazole (ST). Effects of K doping on the textural structure, optical property, band gap and surface chemistry of LaMnO3 are investigated, showing that La0.95K0.05MnO3 (LKMO-5) has the optimal properties. The photoelectric measurements, including photoluminescence (PL), photocurrent response (PCR) and electrochemical impedance spectroscopy (EIS), also suggest that the LKMO-5 has the best electron–hole separation efficiency, the most amounts of irradiated electrons and the lowest impedance. Photocatalytic tests indicate that LKMO-5 not only shows the best activity for CIP degradation, but also exhibits good stability in the reaction, with negligible activity loss within four cycles. Mechanism investigations, explored by the radical trapping experiments and with the reference of band positions, indicate that superoxide radical ions (·O2−) and holes (h+) are the major reactive species of the reaction.

Preliminary Investigation Into the Antidepressant Effects of a Novel Curcumin Analogue (CACN136) In Vitro and In Vivo.

The aim of this study was to develop a novel antidepressant with high activity. Based on the findings of molecular docking, eight novel curcumin analogues were evaluated in vitro to check for antidepressant efficacy. Among them, CACN136 had the strongest antidepressant effect. Firstly, CACN136 had a stronger 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonate) radical ion scavenging ability (IC50: 17.500 ± 0.267μg/mL) compared to ascorbic acid (IC50: 38.858 ± 0.263μg/mL) and curcumin (27.189 ± 0.192μg/mL). Secondly, only CACN136 demonstrated clear protective effects on cells damaged by glutamate and oxidative stress at all concentrations. Finally, only CACN136 showed ASP + inhibition and was more effective than fluoxetine hydrochloride (FLU) at low concentrations. To further confirm the antidepressant effect of CACN136 in vivo, the CUMS model was established. Following 28days of oral administration of CUMS mice, CACN136 increased the central area residence time in the open-field test, significantly increased the sucrose preference rate in the sucrose preference test (P < 0.001) and significantly reduced the immobility period in the tail suspension test (P < 0.0001), all of which were more effective than those of FLU. Subsequent research indicated that the antidepressant properties of CACN136 were linked to a decrease in the metabolism of5-HT and the modulation of oxidative stress levels in vivo. In particular, the activation of the Keap1-Nrf2/BDNF-TrkB signaling pathway by CACN136 resulted in elevated levels of antioxidant enzymes, enhancing the antioxidant capability in mice subjected to CUMS. In conclusion, CACN136 has the potential to treat depression and could be an effective antidepressant.

Antioxidant and Emulsifying Activity of the Exopolymer Produced by Bacillus licheniformis

The exopolymer (ESPp) was obtained from Bacillus licheniformis IDN-EC, composed of a polyglutamic acid and polyglycerol phosphate chain O-substituted with αGal moieties (αGal/αGlcNH2 3:1 molar ratio) and with a 5000 Da molecular weight. The cytotoxicity activity of EPSp was determined by reducing the MTT (3-[4,5-dimethyl-thiazol-2-yl]-2,5-diphenyltetrazolium bromide) to formazan on HeLa cells. This EPS did not show cytotoxicity against the tested cell line. The ESPp presented great advantages as an antioxidant with free radical scavenging activities (1,1-diphenyl-2-picryl-hydrazyl radical (DPPH),hydroxyl radical (OH), and superoxide anion (O2−)) (65 ± 1.2%, 98.7 ± 1.9%, and 97 ± 1.7%), respectively. Moreover, EPSp increased the enzyme activity for catalase (CAT) and glutathione peroxidase (GSH-Px) in HeLa cells (CAT, 2.6 ± 0.24 U/mL; and GSH-Px, 0.75 ± 0.3 U/L). The presence of ESPp showed a significant protective effect against H2O2 in the cell line studied, showing great viability (91.8 ± 2.8, 89.9 ± 2.9, and 93.5 ± 3.6%). The EPSp presented good emulsifying activity, only for vegetable oils, olive oil (50 ± 2.1%) and sesame (72 ± 3%). Sesame was effective compared to commercials products, Triton X-100 (52.38 ± 1.6%), Tween 20 (14.29 ± 1.1%), and sodium dodecyl sulphate (SDS) (52.63 ± 1.6%). Furthermore, the EPS produced at 0.6 M has potential for environmental applications, such as the removal of hazardous materials by emulsification whilst resulting in positive health effects such as antioxidant activity and non-toxicity. EPSp is presented as a good exopolysaccharide for various applications.

Nonadiabatic Photodynamics of Amantadine and 1-Cyanoadamantane Cations.

Cations of diamondoids and derivatives thereof have recently become the subject of experimental, spectroscopic studies due to their potential role in astrochemistry. In particular, their electronic spectra and photoinduced dynamics trigger great interest. Here, we report on computational investigations of two nitrogen-containing derivatives of the adamantane cation (Ada+, C10H16+), the amantadine cation (Ama+, C10H15NH2+) and the 1-cyanoadamantane cation (Ada-CN+, C10H15CN+). Specifically, we study electronic (vibrationally resolved) spectra and nonadiabatic molecular dynamics (modeled using the surface hopping approach based on semiempirical electronic structure theory) of these radical cations. The internal conversion time constants as well as reactive relaxation outcomes (cage-opening and hydrogen loss) are compared for the two derivatives and also with the case of Ada+ [Roy et al., Theor. Chem. Acc.2023, 142, 71]. Remarkably, we find a longer ground-state recovery time for Ada-CN+ than for Ama+ (for the same excitation energy window), despite a smaller excitation energy for the former. Thus, a static energy gap law cannot be used to rationalize nonadiabatic dynamics and excited-state lifetimes in this case: Dynamics and details of the couplings between several states play a decisive role.

Divergent Interaction of (Iso)nitriles with a Linear Iron(I) Silylamide─A Combined Structural, Spectroscopic, and Computational Study.

Nitriles and isonitriles are important σ-donor ligands in coordination chemistry. Isonitriles also function in low-valent complexes as π-acceptor ligands similar to CO. Herein we present the unusual behavior of the highly reducing, high-spin iron(I) complex [Fe(hmds)2]- toward these compound classes. Rare examples of side-on coordination of nitriles to the metal center are observed. Insights gained by 57Fe Mössbauer spectroscopy as well as DFT and CASSCF calculations give an interplay between the resonance structures of not only an iron(I) π-complex and an iron(III) metallacycle but also point to the importance of an iron(II) nitrile radical anion. For an aromatic isonitrile end-on coordination is observed, which is best described as an iron(I) complex with only minor unpaired spin transfer onto the isonitrile. For aliphatic isonitriles, the selective R-CN bond cleavage occurs and yields stoichiometric mixtures of alkyl iron(II) and cyanido iron(II) complexes. Attempts to isolate presumed (iso)nitrile radical anions void of 3d-metal coordination give for the reaction of an aromatic isonitrile with KC8 facile reductive coupling to the corresponding diamido acetylene.

Carbon cloth core with a PEDOT decorated TiO2 shell for degradation of emerging organic contaminants and enhanced vanadium redox flow batteries

In this study, carbon cloth (CC) was enrobed with a TiO2 layer (CC@TiO2) and then decorated with poly(3,4-ethylenedioxythiophene) (PEDOT, CC@TiO2-PEDOT). The XRD, Raman, XPS, and EDS results confirmed the successful preparation of the targeted materials, and SEM images revealed the targeted morphology. According to the UV–vis and PL analysis, the CC@TiO2-PEDOT exhibits wide and strong photoabsorption across the UV–vis spectrum, and the photogenerated charge carriers have a long lifespan and low recombination rate. The photocatalytic assessment revealed that CC@TiO2-PEDOT was more efficient than CC@TiO2 and CC@PEDOT in degrading both benzotriazole and 2-hydroxybenzothiazole, however, 2-hydroxybenzothiazole was more stable than benzotriazole. The superoxide anion radicals, holes, and/or hydroxyl radicals of CC@TiO2-PEDOT played pivotal roles in the photocatalytic degradation of benzotriazole. After the photocatalytic process, the benzotriazole solution was safe to use. The CC@TiO2 and CC@TiO2-PEDOT exhibited a superior performance as a potential cathode for vanadium redox flow batteries (VRFBs) and effectively mitigated the parasitic influence of the hydrogen evolution reaction (HER). CC@TiO2 and CC@TiO2-PEDOT displayed significantly smaller peak separation of 94 and 62 mV, at a scan rate of 5 mV/s, respectively, and a higher suppression for HER in comparison to CC or CC@PEDOT. The performance of the CC@TiO2 and CC@TiO2-PEDOT electrodes manifests their high reversibility for the V(II)/V(III) redox reaction. This research underscores the multifaceted potential of CC@TiO2-PEDOT as a promising material for addressing water purification challenges and advancing VRFBs for sustainable energy applications.

Adjustable optoelectronic properties of triphenylamine-ethylenedioxythiophene based hybrid electrochromic polymer with different electron-donating substituents

Due to the good optoelectronic properties of triphenylamine (TPA) and its derivatives-based organic conjugated polymers, they have been widely used in various organic electronic devices. They are easy to lose electrons to form stable cationic free radicals with color change under electrochemical oxidation conditions. Therefore, TPA derivatives-based electrochromism materials have attracted the widely attentions of researchers. In this work, a series of TPA derivatives were successfully obtained by Stille coupling reactions, and their basic optical and electrical properties were investigated in detail. Their corresponding polymer films (P(TPA-EDOT), P(PhTPA-EDOT), and P(OCH3TPA-EDOT)) were also prepared on transparent ITO glass by electrodeposition method and their electrochromic properties were further studied. Due to the relatively strong electron donating ability of OCH3– group on the TPA unit, the intramolecular charge transfer peak of OCH3TPA-EDOT is obvious red-shifted and its initial oxidation potential is relatively low, which is beneficial for it to get high-quality electrochromic polymers. Electrochemical analysis shows that all these three polymer films show reversible redox reaction with excellent redox stability. Spectroelectrochemistry shows that all of them have good electrochromic properties and show multi-electrochromic behavior with strong color change. The dynamic study show that all these three polymers have relatively fast switching time (as low as 0.8 s), high coloration efficiency (up to 206.2 C−1 cm2) and obvious optical contrast change. Especially in the near infrared region, the optical contrast is relatively high (P(TPA-EDOT) is 45.3 % at 1100 nm, P(PPhTPA-EDOT) is 53.1 % at 1100 nm, and P(OCH3TPA-EDOT) is 57.2 % at 1100 nm). All these results show that the different substituents on the TPA unit have a certain influence on the resultant monomers’ optoelectronic performances, and they also can adjust the optical band gap of the corresponding polymers with different electrochromic properties.

Trans-Selective Carboxylative Cyclization of 1,6-Dienes Using the CO2 Radical Anion

<i>Trans</i>-Selective Carboxylative Cyclization of 1,6-Dienes Using the CO2 Radical Anion

In vitro antioxidant activity, QSAR, in silico toxicity prediction, molecular docking studies, and molecular dynamics of a series of N-ferrocenylmethylanilines as potent antioxidant agents

The superoxide anion radical scavenging activities of a series of twenty-eight ferrocenylmethylaniline derivatives were measured in an in vitro study followed by in silico studies which included quantitative structure-activity relationship (QSAR), toxicity prediction, molecular docking studies, and molecular dynamics simulations. Multilinear regression analysis was employed to establish a quantitative correlation between the scavenging activity of superoxide anion radicals and various structural properties. The QSAR model obtained underwent validation, demonstrating statistical significance with a squared fitting correlation coefficient (R2) of 0.934, an adjusted squared correlation coefficient (R2 adj) value of 0.849, and a cross-validation coefficient (Q2) value of 0.873. Additionally, the calculated Fisher ratio (F) value of 36.525 indicates the model's strong predictability. Toxicity perdition studies demonstrated that among the five most potent compounds, FMA27 and FMA12 were predicted to be non-toxic. The molecular Docking study revealed that compound FMA23 exhibited the least activity against the glutathione reductase enzyme, with the highest inhibitory concentration recorded at 4.16 × 10-6 M and the lowest docking scores observed at -7.34 kcal.mol-1. Interactions between the compound and the amino acid residues of glutathione reductase were primarily hydrophobic and π-cation in nature. Analysis of root mean square deviation (RMSD), radius of gyration (Rg), and root mean square fluctuation (RMSF), from molecular dynamics study, revealed stable fluctuations in protein backbone conformations, consistent compactness of the complex, and minimal fluctuations in most protein residues, respectively.

The nanofiber gel electrolytes with ultra-high ionic conductivity regulated by different acid radical ions for lithium batteries

A nanofiber gel electrolytes with excellent physical properties, electrochemical properties, and cycle life based on poly(vinylidene fluoride)-hexafluoropropylene copolymer modified by magnesium–aluminum bilayered nanosheets (MgAl-LDs) intercalated with different acidic roots ions is prepared by electrostatic spinning. The electrolytes exhibit the best elongation at break of 166 % and tensile strength of 6.59 MPa, and the electrochemical windows are all higher than 5 V. Meanwhile, the ionic conductivity number of nano-GPE intercalated with CO32–, ClO4−, and NO3– reach 5.55*10−3 S/cm, 5.04*10−3 S/cm, and 6.93*10−3 S/cm, respectively. The Li//Li symmetric battery can be stably cycled for more than 1000 h at 1 mA/cm2 with an overpotential of less than 50 mV. The LiFePO4// Li batteries assembled with nano-GPE modified by MgAl-LDs (s = NO3–) show better 0.1-2C multiplicity performance than CO32– and ClO4−, accompanied by an optimal discharge capacity of up to 155 mAhg−1 at 0.1C as well as a high reversible capacity of 135 mAhg−1 and a capacity retention rate of 90 % after 100 cycles at 0.5C. In addition, the results of polarization, X-ray photoelectron spectroscopy (XPS), Computed Tomography (CT), and scanning electron microscope (SEM) tests show that a stable SEI film is formed between nano-GPE and Li anode.

Charge and Spin Transfer Dynamics in a Weakly Coupled Porphyrin Dimer.

The dynamics of electron and spin transfer in the radical cation and photogenerated triplet states of a tetramethylbiphenyl-linked zinc-porphyrin dimer were investigated, so as to test the relevant parameters for the design of a single-molecule spin valve and the creation of a novel platform for the photogeneration of high-multiplicity spin states. We used a combination of multiple techniques, including variable-temperature continuous wave EPR, pulsed proton electron-nuclear double resonance (ENDOR), transient EPR, and optical spectroscopy. The conclusions are further supported by density functional theory (DFT) calculations and comparison to reference compounds. The low-temperature cw-EPR and room-temperature near-IR spectra of the dimer monocation demonstrate that the radical cation is spatially localized on one side of the dimer at any point in time, not coherently delocalized over both porphyrin units. The EPR spectra at 298 K reveal rapid hopping of the radical spin density between both sites of the dimer via reversible intramolecular electron transfer. The hyperfine interactions are modulated by electron transfer and can be quantified using ENDOR spectroscopy. This allowed simulation of the variable-temperature cw-EPR spectra with a two-site exchange model and provided information on the temperature-dependence of the electron transfer rate. The electron transfer rates range from about 10.0 MHz at 200 K to about 53.9 MHz at 298 K. The activation enthalpies Δ‡H of the electron transfer were determined as Δ‡H = 9.55 kJ mol-1 and Δ‡H = 5.67 kJ mol-1 in a 1:1:1 solvent mixture of CD2Cl2/toluene-d8/THF-d8 and in 2-methyltetrahydrofuran, respectively, consistent with a Robin-Day class II mixed valence compound. These results indicate that the interporphyrin electronic coupling in a tetramethylbiphenyl-linked porphyrin dimer is suitable for the backbone of a single-molecule spin valve. Investigation of the spin density distribution of the photogenerated triplet state of the Zn-porphyrin dimer reveals localization of the triplet spin density on a nanosecond time scale on one-half of the dimer at 20 K in 2-methyltetrahydrofuran and at 250 K in a polyvinylcarbazole film. This establishes the porphyrin dimer as a molecular platform for the formation of a localized, photogenerated triplet state on one porphyrin unit that is coupled to a second redox-active, ground-state porphyrin unit, which can be explored for the formation of high-multiplicity spin states.

Electron Transfer in Reaction of 12H-Quinoxalino[2,3-b]phenoxazines with π-Acceptors

Using the reaction of 2,4-di-(tert-butyl)-12-(4-methoxyphenyl)-10-methoxy-12H-quinoxalino[2,3-b]phenoxazine with π-electron acceptors such as tetracyanoquinodimethane and 3,6-di-(tert-butyl)-o-quinone) as an example it was shown that derivatives of this N,O-pentaheterocyclic system are effective electron donors that, under mild conditions, carry out electron transfer reactions with the formation of stable cation and anion radical structures.

Photoinduced Intermolecular Hydroamination and Hydroetherification of Electron-rich Alkenes with Low Catalyst Loadings.

A photochemical method based on visible-light irradiation (blue LEDs/sunlight) has been developed for the intermolecular hydroamination and hydroetherification of electron-rich alkenes. This photochemical method is compatible with a wide range of azoles and electron-rich alkenes, such as vinyl ethers, vinyl sulfides and enamides, and is performed with low concentrations of photocatalyst (1000 ppm). Comprehensive mechanistic studies indicate that this process is initiated by the formation of an active radical cation intermediate through single electron oxidation of azole, which is mediated by excited Acr-Mes+ BF4-.

Phytochemical, Antimicrobial, and Antioxidant Activity of Different Extracts from Frozen, Freeze-Dried, and Oven-Dried Jostaberries Grown in Moldova

In this paper, the qualitative and quantitative profile is evaluated of the bioactive compounds, antioxidant activity (AA), microbiostatic properties, as well as the color parameters of jostaberry extracts, obtained from frozen (FJ), freeze-dried (FDJ), and oven-dried berries (DJ). The optimal extraction conditions by ultrasound-assisted extraction (UAE) and microwave-assisted extraction (MAE) were selected after determination of the total polyphenol content (TPC), total flavonoid content (TFC), total antocyanin content (TA), AA by 2,2-diphenyl-1-picrylhydrazyl-hydrate (DPPH), and the free radical cation 2,2-azinobis-3-ethylbenzothiazoline-6-sulfonates (ABTS). Non-conventional extraction methods are less destructive to anthocyanins, while drying the berries reduced TA, regardless of the extraction method. The oven-drying process reduced the concentration of TA in DJ extracts by 99.4% and of ascorbic acid by 92.42% compared to FJ. AA was influenced by the jostaberry pretreatment methods. The DPPH and ABTS tests recorded values (mg Trolox equivalent/g dry weight) between 17.60 and 35.26 and 35.64 and 109.17 for FJ extracts, between 7.50 and 7.96 and 45.73 and 82.22 for FDJ, as well as between 6.31 and 7.40 and 34.04 and 52.20 for DJ, respectively. The jostaberry pretreatment produced significant changes in all color parameters. Mutual information analysis, applied to determine the influence of ultrasound and microwave durations on TPC, TFC, TA, AA, pH, and color parameters in jostaberry extracts, showed the greatest influence on TA (0.367 bits) and TFC (0.329 bits). The DPPH and ABTS inhibition capacity of all FJ’ extracts had higher values and varied more strongly, depending on pH, heat treatment, and storage time, compared to the AA values of FDJ’ and DJ’ extracts. A significant antimicrobial effect was observed on all bacterial strains studied for FJP. FDJP was more active on Bacillus cereus, Staphylococcus aureus, and Escherichia coli. DJP was more active on Salmonella Abony and Pseudomonas aeruginosa. The antifungal effect of DJP was stronger compared to FDJP. Jostaberry extracts obtained under different conditions can be used in food production, offering a wide spectrum of red hues.

Charge Density Study of Two-Electron Four-Center Bonding in a Dimer of Tetracyanoethylene Radical Anions as a Benchmark for Two-Electron Multicenter Bonding

Charge Density Study of Two-Electron Four-Center Bonding in a Dimer of Tetracyanoethylene Radical Anions as a Benchmark for Two-Electron Multicenter Bonding

Investigation on the Potential of Some N-phenylalkanehydrazides as Superoxide Anion Radical Scavengers and Glutathione Peroxidase Binders with ADME Prediction: Comparison with Vitamin C

Objective: An investigation on the antioxidant activity and ADME properties of some N-phenylalkanehydrazides (NPhs) in comparison with ascorbic acid was carried out. Materials and Methods: The power of the compounds to scavenge the superoxide anion radical was examined using cyclic voltammetry. Furthermore, molecular docking was used to examine how NPhs bind to the antioxidant enzyme glutathione peroxidase (GPx). Finally, ADME properties were predicted using the SwissADME webserver. Results: The results showed that the studied compounds had significantly higher EC50 values than Vitamin C and displayed spontaneous binding with GPx with binding energy similar to ascorbic acid. Also, substantial values emerged from the predictive analysis of drug-likeness and bioavailability characteristics. Discussion: First, the EC50 of the compounds under study was determined by assessing the decrease in the anodic current peak intensity; this demonstrated significant radical scavenging activity. Next, the electrostatic way of binding with ROS radical and with antioxidant enzyme was disclosed by the binding free energies; however, the oxygen and nitrogen atoms in the compounds' structures might make many conventional hydrogen bonds with amino acids. Finally, NPh (a) followed all the rules for drug-likeness and bioavailability estimates, making it a promising moiety for synthesising new antioxidant chemicals. Conclusion: The current study is a hybrid of experimental and computational methods that complement each other perfectly.