Radical Formation Research Articles

Photoredox-Catalysis Fluorosulfonyldifluoromethylation of Unactivated Alkenes and (Hetero)arenes with ICF2SO2F.

The fluorosulfonyldifluoromethylation of unactivated alkenes and (hetero)arenes with iododifluoromethanesulfonyl fluoride (ICF2SO2F) under visible light photoredox catalysis was successfully developed. Key to the successful fluorosulfonyldifluoromethylation of aromatic compounds was the usage of AgOTf as an additive to promote the formation of the CF2SO2F radical. The protocol provided a straightforward way to introduce the interesting and useful CF2SO2F group on sp3 and sp2 carbons.

Photocatalyzed 1,3-Bromodifluoroallylation of [1.1.1]Propellane with α-Trifluoromethylalkenes and KBr Salts.

Herein we unveil a visible-light-driven transition-metal-free 1,3-bromodifluoroallylation of [1.1.1]propellane. This reactivity is harnessed through organophotocatalysis, providing practical synthetic pathways to 1-brominated-3-gem-difluoroallylic bicyclo[1.1.1]pentane derivatives, particularly derived from readily available α-trifluoromethylalkenes and inexpensive KBr salts utilized as precursors for bromine radicals. Mechanistic investigations reveal that bromide anions quench the excited state of the photocatalyst, leading to the formation of bromine radicals, which react in a strain-release radical addition process rather than hydrogen atom abstraction with [1.1.1]propellane.

Photocatalytic Cross-Coupling of Aldehydes and Alkenes for Aryl Vinyl Ketones by a Single Catalyst.

Herein is the first example of photocatalytic cross-coupling of alkenes with aldehydes by a single catalyst without an external photosensitizer and any additives. Irradiation of the aromatic aldehyde and cobaloxime catalyst results in the formation of an acyl radical, which undergoes radical addition with alkene or indole and subsequently β-H elimination to afford alkenyl ketone. The reaction features cheap and readily available raw materials, a broad substrate scope, and mild conditions, even for late-stage derivatization of bioactive compounds.

Protective Role of Polyethylene Glycol Towards the Damaging Effects of Cadmium.

This study aimed to evaluate the role of drought-induced changes in the effects of cadmium (Cd) in plants. Cd is the most hazardous and important environmental pollutant. Water deficit is the most common environmental stress encountered by plants and affects most of the plant functions. The present study assessed the effect of Cd and water deficit on Capsicum frutescens seedlings in single and combined treatments. The seedlings of Capsicum were grown in a hydroponic solution and treated with Cd. The seedlings were subjected to water deficit with the help of polyethylene glycol (PEG). The other set of seedlings was treated with combined Cd + PEG. In the absence of PEG, maximum Cd accumulation was observed. The root and shoot growth of the seedlings were affected under all treatments with maximum inhibition in Cd. Pigment, protein and sugar contents and nitrate reductase activity decreased significantly in all treatments, while proline content increased. Induction of oxidative damage occurred through the formation of free radicals which caused alteration in electrolyte leakage, lipid peroxidation and activities of antioxidant enzymes, viz. superoxide dismutase, catalase, ascorbate peroxidase, guaiacol peroxidase and non-enzymatic non-protein thiol content and ascorbic acid in the stressed seedlings. Water deficit buttressed the toxic effect of Cd on chilli seedlings.

Activating Fenton-like reaction by hydrochars containing persistent free radicals derived from various pomelo peel components

To reveal the influence of the diversity of precursors on the formation of environmental persistent free radicals (EPFRs), pomelo peel (PP) and its physically divided portion, pomelo cuticle (PC), and white fiber (WF) were used as precursors to prepare six hydrochars: PPH-Fe, PCH-Fe, WFH-Fe, PPH, PCH, and WFH with and without Fe(III) addition during hydrothermal carbonization (HTC). PPH-Fe and WFH-Fe had higher EPFRs content (9.11 × 1018 and 8.25 × 1018 spins·g−1) compared to PPH and WFH (3.33 × 1018 and 2.96 × 1018 spins·g−1), indicating that iron-doping favored EPFRs formation. However, PCH-Fe had lower EPFRs content (2.78 × 1018 spins·g−1) than PCH (7.95 × 1018 spins·g−1), possibly due to excessive iron leading to the consumption of the generated EPFRs. For another reason, the required Fe(III) amount for EPFRs formation might vary among different precursors. PC has a lower concentration of phenolic compounds but 68–97% fatty acids, while WF and PP are rich in cellulose and lignin. In the Fenton-like reaction, oxygen-centered radicals of hydrochar played a significant role in activating H2O2 and efficiently degrading bisphenol A (BPA). Mechanisms of reactive oxygen species (ROS) generation in hydrochar/H2O2 system were proposed. EPFRs on hydrochar activate H2O2 via electron transfer, creating ·OH and 1O2, leading to BPA degradation. More importantly, the embedded EPFRs on the hydrochar's inner surface contributed to the prolonged Fenton-like reactivity of PPH-Fe stored for 45 days. This study demonstrates that by optimizing precursor selection and iron doping, hydrochars can be engineered to maximize their EPFRs content and reactivity, providing a cost-effective solution for the degradation of hazardous pollutants.Graphical abstract

Electrochemical radical cation aza-Wacker cyclizations

Electrochemical or photochemical single-electron oxidation of bench-stable substrates can generate radical cations that offer unique reactivities as intermediates in various bond-formation processes. Such intermediates can potentially take part in both radical and ionic bond formation; however, the mechanisms involved are complicated and not fully understood. Herein, we report electrochemical radical cation aza-Wacker cyclizations under acidic conditions, which are expected to proceed via radical cations generated by single-electron oxidation of alkenes.

Native and TMT Chestnut Extractives as Hydrophobic and Photostabylizing Additives for Wood Surfaces

Wood extractives have proven strong anti-oxidative properties which may be used to mitigate surface deterioration caused by photolytic effects and free radical formations. An interesting challenge regarding wood extractives is understanding how they behave in terms of treating natural wood surfaces to reduce anti-oxidative processes that arise from exposure to the main environmental factors. In this study, the possible efficacy of chestnut (Castanea sativa Mill.) extractives derived from native (CH) and thermally modified wood (TMT CH), as a means of protecting against UV exposure in poplar (Populus spp.) and spruce (Picea abies Karst.) wood, was evaluated. Chestnut wood was first thermally modified at 180 °C for 3 h, and the extractives were obtained by the accelerated solvent extraction technique (ASE) and subsequently used to treat wood surfaces. Samples were immersed in extractive solutions and exposed to artificial UV-weathering exposure, then contact angle and colour stability were monitored during the process. An FTIR analysis of the photo-degradation process of poplar and spruce surfaces was also executed. Extractives of TMT chestnut changed the total colour variation in both poplar and spruce wood. A much darker colour compared to the extractives of native wood was observed and an increase in ∆E* from 9.75 to 30.76 and 6.24 to 22.97 in poplar and spruce was calculated. The stability of the colour depended both on the surface wood and the type of extractive. The initial contact angle remained almost unchanged in the poplar wood surface and only slightly increased in spruce regardless of whether they were treated with extractives from native or TMT chestnut wood. A strong reduction in contact angle after the accelerated UV exposure test was observed, especially in spruce treated with CH extractives. FTIR analysis confirmed the lower levels of chemical degradation of surfaces observed by colorimetry, where TMT CH extractives formed more stable chemical bonds than native extractives. The comparative analysis in this study clarified the complex relationships between the effects of high-temperature modification of wood and the potential protective role of TMT extractives on some wood surfaces.

Heme-catalyzed degradation of linoleate 9-hydroperoxide (9-HPODE) forms two allylic epoxy-ketones via a proposed pseudo-symmetrical diepoxy radical intermediate

Heme-initiated decomposition of unsaturated fatty acid hydroperoxides creates alkoxyl radicals that propagate a complex series of reactions to hydroxy, keto, epoxy and aldehydic products. Herein, among the products from the hematin-catalyzed degradation of 9-hydroperoxy-linoleic acid (9-HPODE), we observed a double peak on normal-phase HPLC that resolved on RP-HPLC into equal proportions of two epoxy-allylic ketones with identical UV spectra. Their proton NMR spectra were also indistinguishable and consistent with 9,10-trans-epoxy-11E-13-keto- and 9-keto-10E-12,13-trans-epoxy-octadecenoic acids. Acid hydrolysis to the corresponding dihydroxy-ketones and GC-MS analysis identified the earlier eluting product on RP-HPLC as the 9,10-epoxy regio-isomer. Starting from the C9-hydroperoxide, recovery of the two epoxy-ketones in equal proportions suggests their formation from a common intermediate. Earlier work has proposed formation of a pseudo-symmetrical diepoxy radical (9,10-epoxy-11(•)-12,13-epoxy, derived from an epoxy allylic hydroperoxide precursor) in the carbon chain fragmentation leading to aldehydic products. This intermediate in pathways of alkoxyl radical reactions forms equal pairs of aldehydes, and now also a pair of epoxy-ketones, and based on mechanism the same products arise from either 9-HPODE or 13-HPODE. Our results point to the intermediacy of this diepoxy-carbinyl radical in the origin of at least two classes of linoleate peroxidation products, and it should be considered as a viable intermediate for homo-conjugated diene peroxidation in general. The reactions could contribute to the aldehydes and epoxy-ketones in tissues undergoing oxidative transformations of polyunsaturated fatty acids.

Residential Wood Burning and Vehicle Emissions as Major Sources of Environmentally Persistent Free Radicals in Fairbanks, Alaska.

Environmentally persistent free radicals (EPFRs) play an important role in aerosol effects on air quality and public health, but their atmospheric abundance and sources are poorly understood. We measured EPFRs contained in PM2.5 collected in Fairbanks, Alaska, in winter 2022. We find that EPFR concentrations were enhanced during surface-based inversion and correlate strongly with incomplete combustion markers, including carbon monoxide and elemental carbon (R2 > 0.75). EPFRs exhibit moderately good correlations with PAHs, biomass burning organic aerosols, and potassium (R2 > 0.4). We also observe strong correlations of EPFRs with hydrocarbon-like organic aerosols, Fe and Ti (R2 > 0.6), and single-particle mass spectrometry measurements reveal internal mixing of PAHs, with potassium and iron. These results suggest that residential wood burning and vehicle tailpipes are major sources of EPFRs and nontailpipe emissions, such as brake wear and road dust, may contribute to the stabilization of EPFRs. Exposure to the observed EPFR concentrations (18 ± 12 pmol m-3) would be equivalent to smoking ∼0.4-1 cigarette daily. Very strong correlations (R2 > 0.8) of EPFR with hydroxyl radical formation in surrogate lung fluid indicate that exposure to EPFRs may induce oxidative stress in the human respiratory tract.

Identifying Mechanisms and Challenges for Electrochemical Oxidation of Cyclohexane to KA Oil

Electrochemical oxidation of cyclohexane to KA oil, a mixture of cyclohexanone and cyclohexanol, holds great promise for decarbonized chemical manufacturing based on the value of products and the thermodynamic equilibrium potential. However, fundamental understanding of this reaction is extremely limited. For example, even the number of electrons in this reaction has not yet been identified. In this work, we elucidate the mechanism of electrochemical cyclohexane oxidation to KA oil on fluorine-doped tin oxide (FTO), platinum, and glassy carbon anodes. Using three-electrode electroanalysis, isotopic labeling, and concentration studies, we show that electrochemical cyclohexane oxidation to KA oil is similar to its thermochemical analogue in that O2, not water, is the primary oxygen source. The reaction is initiated through the formation of cyclohexyl or hydroxyl radicals, depending on electrode and electrolyte composition. Additionally, crossover from undivided two-electrode cells is found to impact measurements such that cathodic reaction and reactor design may introduce potential artifacts to anodic activity and selectivity. These findings have significant implications for the technological viability of a theoretically promising electrosynthesis process.

Transforming Sunlight through Ultrasonically Engineered ZnO and g-C₃N₄ Z-Scheme Heterostructure for Superior Photocatalysis: Experimental and Theoretical Study

In this study, we enhanced ZnO photocatalytic activity by synthesizing nanostructures with high aspect ratio of exposed polar facets. Post-synthesis ultrasonication induced morphological reconfiguration, improving optoelectronic properties, charge carrier separation, photocurrent, and shifted the valence band edge potential to higher positive values, providing a heightened overpotential for hydroxyl radical formation. The resulting overpotential for hydroxyl radical formation significantly boosted phenol degradation under UV light. To extend photoresponse, we employed ultrasonication to create a direct Z-scheme heterostructure with gCN, preventing particle aggregation. The S-ZnO/gCN photocatalyst, exhibiting a highly ordered structure, demonstrated superior photocatalytic activity under solar light for phenol degradation. Experimental results showed that increased dissolved oxygen accelerated hydroquinone and catechol formation, enhancing phenol degradation. Experimental results were supported by theoretical calculations. This innovative approach not only improves ZnO photocatalytic activity but also broadens its application to solar light-driven reactions.

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.

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.

TBuOK/TMSOK‐Mediated “Alkyl Halide to Alkyl Free Radical” Transformation for Transition‐Metal‐Free Benzoin α‐C—H Alkylation

Comprehensive SummaryThe alkali tert‐butoxide (tBuOK or tBuONa) mediated generation of aryl free radical from aryl iodide remarks a milestone discovery in the free radical chemistry. However, the equivalent “alkyl halide to alkyl free radical” transformation has not yet been realized in applicable synthesis by similar catalytic tactic. In this paper, the first practical “alkyl halide to alkyl free radical” transformation mediated by tBuOK or TMSOK in the direct α‐C—H alkylation of benzoins is presented. As the parallelly significant issue as aryl free radical generation, the current work, while bringing a rather facile and useful new approach for the synthesis of diverse benzoins, represents also an important step in the alkyl free radical‐based synthesis by displaying the higher generality of simple alkali base mediated radical formation.

Bisphosphonium Benzene Diimides.

The incorporation of cationic groups onto electron-poor compounds is a viable strategy for achieving potent electron acceptors, as evidenced by reports of air-stable radical forms of large aromatic diimides such as naphthalene and perylene diimides. These ions have also been observed to exhibit anion-π interaction tendencies of interest in molecular recognition applications. The benefits of phosphonium incorporation, however, have not yet been extended to the smallest benzene diimides. Here, we report that dibrominated pyromellitic diimide and mellophanic diimide both readily undergo substitution reactions with phosphine sources to yield bisphosphonium compounds. In the single crystalline form, these dications display anion-π interactions and, in the case of mellophanic diimide, the stabilization of a bromide-water H-bonding ring pattern. The reaction of these dications with chemical reductants readily provides the singly and doubly reduced redox states, which were characterized by UV-vis spectroscopy and found to exhibit intense absorptions extending into the near-IR region. Taken together, this work demonstrates that phosphonium incorporation onto congested aromatic diimide scaffolds is synthetically viable and produces unusual electron-poor compounds.

The degradation of tetrabromobisphenol A by metal-free graphene oxide in the dark

Brominated flame retardants (BFRs) such as tetrabromobisphenol A (TBBPA) were widely detected in the environment. The ease of synthesis of graphene-based materials (GBMs) makes it an excellent metal-free carbon-based catalyst for the reductive debromination of TBBPA. Here we explore the complete debromination of TBBPA from the aqueous environment in the dark using metal-free graphene oxide (GO) and reduced GO (rGO). More importantly, radical scavenger experiments reveal the formation of superoxide radicals and singlet oxygen from the surface of GBMs leading to the debromination of TBBPA. GO shows an enhanced catalytic activity due to enriched O-functional groups on the surface than rGO, as observed by cyclic voltammetry and electrochemical impedance spectroscopy. In addition, the TBBPA degradation pathway was proposed with BPA as the end product and by-products were identified by mass spectroscopy. The complete TBBPA degradation was observed within 240 mins of reaction time (kobs = 8.6×10−3 min−1), which was significantly more efficient than the catalytic activity of other metal-based catalysts. Our study thus provides a new insight into the debromination mechanisms of TBBPA which would exhibit potential for future efficient catalyst development.

The Increase in the Peroxidase Activity of the Cytochrome C with Substitutions in the Universal Binding Site Is Associated with Changes in the Ability to Interact with External Ligands

Cytochrome c (CytC), a one-electron carrier, transfers electrons from complex bc1 to cytochrome c oxidase (CcO) in the electron-transport chain. Electrostatic interaction with the partners, complex bc1 and CcO, is ensured by a lysine cluster near the heme forming the Universal Binding Site (UBS). We constructed three mutant variants of mitochondrial CytC with one (2Mut), four (5Mut), and five (8Mut) Lys->Glu substitutions in the UBS and some compensating Glu->Lys substitutions at the periphery of the UBS for charge compensation. All mutants showed a 4–6 times increased peroxidase activity and accelerated binding of cyanide to the ferric heme of CytC. In contrast, decomposition of the cyanide complex with ferrous CytC, as monitored by magnetic circular dichroism spectroscopy, was slower in mutants compared to WT. Molecular dynamic simulations revealed the increase in the fluctuations of Cα atoms of individual residues of mutant CytC compared to WT, especially in the Ω-loop (70–85), which can cause destabilization of the Fe…S(Met80) coordination link, facilitation of the binding of exogenous ligands cyanide and peroxide, and an increase in peroxidase activity. It was found that only one substitution K72E is enough to induce all these changes, indicating the significance of K72 and the Ω-loop (70–85) for the structure and physiology of mitochondrial CytC. In this work, we also propose using a ferro-ferricyanide buffer as a substrate to monitor the peroxidase activity of CytC. This new approach allows us to determine the rate of peroxidase activity at moderate (200 µM) concentrations of H2O2 and avoid complications of radical formation during the reaction.

A General Copper-Box System for the Asymmetric Arylative Functionalization of Benzylic, Propargylic or Allenylic Radicals.

Radical-involved arylative cross-coupling reactions have recently emerged as an attractive strategy to access valuable aryl-substituted motifs. However, there still exist several challenges such as limited scope of radical precursors/acceptors, and lack of general asymmetric catalytic systems, especially regarding the multicomponent variants. Herein, we reported a general copper-Box system for asymmetric three-component arylative radical cross-coupling of vinylarenes and 1,3-enynes, with oxime carbonates and aryl boronic acids. The reactions proceed under practical conditions in the absence or presence of visible-light irradiation, affording chiral 1,1-diarylalkanes, benzylic alkynes and allenes with good enantioselectivities. Mechanistic studies imply that the copper/Box complexes play a dual role in both radical generation and ensuing asymmetric cross-coupling. In the cases of 1,3-enynes, visible-light irradiation could improve the activity of copper/Box complex toward the initial radical generation, enabling better efficiency match between radical formation and cross-coupling.

CH4-NH3-NO oxidation: The interplaying role of NO sensitizing effect and DeNOx chemistry

This work presents a systematic experimental and numerical investigation of the oxidation behavior of fuel-lean CH4-NH3-NO mixtures in a Jet Stirred Flow Reactor. The experimental tests were performed as a function of the mixture preheating temperature (750–1250 K), at fuel-lean conditions (0.8), changing the concentration of ammonia in the fuel blends (from 0 up to 70 %). Results showed a significant sensitizing effect of NO on the oxidation of methane and methane/ammonia mixtures. In particular, CH4 reactivity is drastically enhanced by NO additions, while the onset of oxidation is gradually shifted to higher preheating temperatures as the concentration of NH3 increases.The kinetic analyses suggested that the interaction of NO with C-chemistry explicates through the reaction loop NO+HO2=NO2+OH and CH3+NO2=CH3O+NO, which influences both the reactivity and the thermo-kinetic instabilities, by promoting the formation of OH radicals and activating the CH3O oxidation pathway. Specifically, the NO-NO2 loop is identified as a crucial factor when the branching chemistry involves HO2 radicals.The presence of NH3 counterbalances this sensitizing effect through the activation of DeNOx chemistry, which partially inhibits the NO-NO2 -loop since they both compete for the NO consumption. In addition, NH3 can act as OH scavenger through NH3+OH=NH2+H2O, hindering the CH4 conversion via CH4+OH=CH3+H2O, thus slowing down the overall mixture reactivity.

Qualitative Analysis and Anti-oxidant Potential of Ethanolic Extract ofManilkara zapota (L.) P. Royen Leaves

Background: The normal metabolic functioning of aerobic cells is related to free radical formation. The oxygen utilized in the cell growth gives rise to a number of oxygen free radicals. Further, these oxygen free radicals interact with lipidic molecules to produce hydroxyperoxides and various other peroxides also, radicals like superoxide, hydroxyls, and lipoid peroxides, which lead to cytotoxicity due to their interaction with biological systems. The uncontrolled generation of free radicals may lead to various diseases and disorders like prostate cancer, coronary heart disease and also ageing. The therapeutic potential of the plant M. zapota has been demonstrated in various diseases, such as cancers (e.g., breast, prostate, cervical, and hepatocellular cancer), diabetes mellitus, arthritis, bacterial infections, and gastrointestinal disorders (e.g., diarrhea and ulcers) and many medical conditions. The main phytocomponents of this plant are polyphenols, alkaloids, glycosides, flavonoids, saponins, triterpenoids, carbohydrates, tannins, and sterols. Objective: The objective of this study is to investigate qualitative analysis and anti-oxidant potential of ethanolic extract of Manilkara zapota (L.) P. Royen Leaves. In demand to minimize the damage caused by free radicals. It is very essential to develop such antioxidants which protect the body from the effect of free radicals and also do not cause much harm to the human body. The main phytocomponents of the plant are polyphenols, alkaloids, glycosides, flavonoids, saponins, triterpenoids, carbohydrates, tannins and sterols which are responsible for antioxidant activity. Materials and Methods: Phytochemical screening methods, Gas chromatography–mass spectrometry (GC-MS), Fourier transform infrared (FTIR), and Hydrogen Peroxide scavenging assay for analysis of an ethanolic extract of plant leaves. Results and Discussion: Antioxidant activity was determined by a hydrogen peroxide assay. Plant extract was examined using phytochemical screening, GC-MS analysis, and FTIR spectra. The plant extract showed hydrogen peroxide scavenging activity (IC50 = 16.45 μg/ml) compared to the IC50 values of standard ascorbic acid (IC50 = 9.079 μg/ml). Conclusion: The present study concluded the antioxidant and phytochemical assessment of the ethanolic extract of the leaves of Manilkara zapota. The results of the present research study demonstrated that the antioxidant activity of the plant extract was strong as compared to ascorbic acid.