Generation Of Superoxide Radicals Research Articles

Designing copper-doped zinc oxide nanoparticle by tobacco stem extract-mediated green synthesis for solar cell efficiency and photocatalytic degradation of methylene blue

This study presents the green synthesis of copper-doped zinc oxide (Cu-doped ZnO) nanoparticles using tobacco stem (TS) extract. The environmentally friendly synthesis method ensures distinct features, high efficiency, and applicability in various fields, particularly in solar cell technology and photocatalytic applications. ZnO nanostructures are investigated due to their unique properties, cost-effectiveness, and broad range of applications. The nanoparticles are synthesized with varying Cu concentrations, and their structural, morphological, and compositional characteristics are thoroughly analyzed. The Cu-doped ZnO nanoparticles exhibit improved properties, such as increased surface area and reduced particle size, attributed to the incorporation of Cu dopants. The green synthesis approach using TS extract serves as a stabilizing agent and avoids the toxicity associated with chemical methods. Characterization techniques including SEM, TEM, EDX, FTIR, and XRD confirm the successful synthesis of the nanoparticles. Photocatalytic degradation studies reveal that the 5% Cu-doped ZnO exhibits the highest photocatalytic activity against methylene blue, attributed to synergistic effects between Cu and ZnO, including oxygen vacancy and electron–hole pair recombination rate suppression. The photocatalytic mechanism involves the generation of superoxide and hydroxyl radicals, leading to methylene blue degradation. Furthermore, the Cu-doped ZnO nanoparticles demonstrate promising photovoltaic performance, with the optimal efficiency observed at a 5% Cu concentration. The study suggests that Cu-doped ZnO has the potential to enhance solar cell efficiency and could serve as an alternative material in solar cell applications. Future research should focus on refining Cu-doped ZnO for further improvements in solar energy conversion efficiency

Autocatalytic degradation of Cu-EDTA in the Calcite/PMS system: Singlet oxygen and Cu(III)

The simultaneous removal of heavy metal complexes (HMCs) and heavy metal ions presents a significant challenge in treating wastewater. To address this, we propose a Calcite/Peroxymonosulfate (Calcite/PMS) system aimed at simultaneously decomplexing Cu-EDTA and removing Cu ions. Calcite/PMS system could achieve 99.5 % Cu-EDTA decomplexation and 61.9 % Cu ions removal within 60 min under initial conditions of Cu-EDTA (10 mg/L), Calcite (3 g/L), and PMS (2 mM). Singlet oxygen (1O2) emerged as the predominant reactive species responsible for Cu-EDTA decomplexation, which selectively targeted the N-C bonds in the Cu-EDTA structure to produce intermediates with lower biotoxicity than EDTA. Interestingly, solid phase Cu(III) (≡Cu(III)) promoted the generation of superoxide radicals (O2•−) with a contribution of up to 72.8 %. Subsequently, nascent ≡Cu(III) and O2•− accelerated the degradation of intermediates. Besides, coexisting organic substances inhibited Cu-EDTA decomplexation, whereas inorganic ions had a weak impact. After five cycles of use, the Calcite/PMS system retained 99.3 % efficiency in decomplexing Cu-EDTA. This investigation provides valuable insights into using calcite to remove HMCs and enhances our comprehension of the decomplexation intermediates accelerating HMCs degradation.

A Copper Silicate-Based Multifunctional Nanoplatform with Glutathione Depletion and Hypoxia Relief for Synergistic Photodynamic/Chemodynamic Therapy.

Chemodynamic therapy (CDT) alone cannot achieve sufficient therapeutic effects due to the excessive glutathione (GSH) and hypoxia in the tumor microenvironment (TME). Developing a novel strategy to improve efficiency is urgently needed. Herein, we prepared a copper silicate nanoplatform (CSNP) derived from colloidal silica. The Cu(II) in CSNP can be reduced to Cu(I), which cascades to induce a subsequent CDT process. Additionally, benefiting from GSH depletion and oxygen (O2) generation under 660 nm laser irradiation, CSNP exhibits both Fenton-like and hypoxia-alleviating activities, contributing to the effective generation of superoxide anion radical (•O2-) and hydroxyl radical (•OH) in the TME. Furthermore, given the suitable band-gap characteristic and excellent photochemical properties, CSNP can also serve as an efficient type-I photosensitizer for photodynamic therapy (PDT). The synergistic CDT/PDT activity of CSNP presents an efficient antitumor effect and biosecurity in both in vitro and in vivo experiments. The development of an all-in-one nanoplatform that integrates Fenton-like and photosensing properties could improve ROS production within tumors. This study highlights the potential of silicate nanomaterials in cancer treatment.

Tunable multicolor supramolecular assemblies based on phosphorescence cascade energy transfer for photocatalytic organic conversion and anti-counterfeiting

Making full use of the captured energy by phosphorescence light-harvesting systems (PLHSs) and the tunable photoluminescence in energy transfer process to realize the multiple applications is still the challenge of PLHSs research. In this study, we have successfully constructed a highly effective PLHS with tunable multicolor luminescence and efficient conversion of photosensitizer types, which can further be used in photocatalytic organic conversion, information anti-counterfeiting and storage. The supramolecular polymer of BDBP-CB[8], which is generated by cucurbit[8]uril (CB[8]) and 4-(4-bromophenyl)-pyridine derivative (BDBP), realizes a phosphorescence emission and a change in luminescence color. Notably, white light emission was achieved and the logic gate systems were constructed utilizing the application of adjustable luminescence color. More interestingly, PLHS can be constructed by employing BDBP-CB[8] as energy donors, Sulforhodamine 101 (SR101) and Cyanine5 (Cy5) as energy acceptors, which results in a remarkably tunable multicolor photoluminescence to achieve the information storage. Furthermore, we have also found that BDBP-CB[8] can serve as type II photosensitizer for the effective production of singlet oxygen (1O2) during the photooxidation process of styrene in aqueous environments, attaining a remarkable output rate reaching as high as 89 %. Particularly, compared with 1O2 produced by type II photosensitizer BDBP-CB[8], the construction of PLHS can effectively convert type II photosensitizer to type I photosensitizer and efficiently generate superoxide anion radical (O2•−), which can be used for photocatalytic cross-dehydrogenative coupling (CDC) reaction in the aqueous solution with a yield of 90 %. Thus, we have created a PLHS that not only achieves tunable multicolor emission for information anti-counterfeiting and storage, but also realizes the conversion of reactive oxygen species (ROS) for different types photocatalytic oxidation reactions.

Fully conjugated radical-doped COF for near-infrared photothermal conversion, C-3 thiocyanation of indoles and oxidative coupling of amines

Radical-doped covalent organic frameworks (COFs) have received much interest as it confers additional functions such as photomodulated electrical conductivity, magnetism, and photochromism. Such COFs are relatively underexplored, however, mainly due to the lack of suitable highly photoactive building blocks. Herein, a rare radical-doped fully conjugated COF (PDI-COF) was rationally designed and prepared by incorporating photoactive perylenediimides (PDIs) into its framework. Characterization of the product PDI-COF not only confirmed its porous and stable skeleton, but also revealed the radical derived from photoinduced electron transfer between the PDI and electron donor. The fully conjugated and radical-doped characteristics enable the effective realization of near-infrared photothermal conversion in this COF. Moreover, this radical-doped COF can efficiently generate superoxide radical anions under light irradiation, which promote the photocatalytic C-3 thiocyanation of indoles and the oxidative coupling of amines in high yield and good recyclability at room temperature and without additives. This study demonstrates that introducing a photoactive organic dye into a COF is an effective approach to photothermal conversion materials and metal-free porous photocatalysts for application in photothermal therapy and photocatalytic organic synthesis.

Built-in electric field mediated S-scheme charge migration and Co-N4(II) sites in cobalt phthalocyanine/MIL-68(In)-NH2 heterojunction for boosting photocatalytic nitric oxide oxidation

The efficiency of photocatalytic Nitric Oxide(NO) oxidation is limited by the lack of oxygen(O2) active sites and poor charge carrier separation. To address this challenge, we developed a molecular Cobalt Phthalocyanine modified MIL-68(In)–NH2 photocatalyst with a robust Built-in electric field(BIEF). In the 2 % CoPc-MIN sample, the BIEF strength is increased by 3.54 times and 5.83 times compared to pristine CoPc and MIL-68(In)–NH2, respectively. This BIEF facilitates the efficient S-scheme charge transfer, thereby enhancing photogenerated carrier separation. Additionally, the Co-N4(II) sites in CoPc can effectively trap the separated photoexcited electrons in the S-scheme system. In addition, the Co-N4(II) sites can also serve as active sites for O2 adsorption and activation, promoting the generation of superoxide radical (O2–), thereby driving the direct conversion of NO to nitrate(NO3–). Consequently, the 2 % CoPc-MIN sample exhibits a remarkable photocatalytic NO removal efficiency of 79.37 % while effectively suppressing the formation of harmful by-product nitrogen dioxide(NO2) to below 3.5 ppb. This study provides a feasible strategy for designing high-efficiency O2 activation photocatalysts for NO oxidation.

Mechanical milling assisted synthesis of FePc-gCN nanocomposite photocatalyst: Dye degradation, mechanism and DFT insights

We present here a mechanochemical method for facile synthesis of Iron phthalocyanine (FePc)- graphitic carbon nitride (gCN) composite with varying weight ratio (1:1, 1:2.5, 1:5) of FePc and gCN. The photocatalytic efficiency of FePc-gCN composite for the elimination of various synthetic dyes, viz, Methylene Blue (MB), Congo Red (CR) and Eosin B (EB) in aqueous media were investigated under visible radiation. The sample with FePc:gCN weight ratio of 1:5 resulted in a removal efficiency of 90 % for MB and 75 % for EB, much higher than their individual counterparts. The synergistic interaction, less charge recombination, and smaller charge transfer resistance in FePc-gCN composite contributed to the superior catalytic performances as confirmed from the impedance spectroscopy and the photoluminescence spectroscopy. Moreover, first principle based DFT calculations on the O2 adsorbed FePc-gCN heterostructure predicted a net transfer of |0.11e| charges from Fe to O atom, favoring the generation of super oxide (O2•−) radicals which contributes actively towards degradation of dye pollutants.

Sustainable photoelectrocatalytic oxidation of antibiotics using Ag–CoFe2O4@TiO2 heteronanostructures for eco-friendly wastewater remediation

Developing high-performance and durable catalysts presents a significant challenge for oxidizing toxic inorganic and pharmaceutical compounds in wastewater. Recently, there has been a surge in the development of new heterogeneous catalysts for degrading pharmaceutical compounds, driven by advancements in electrocatalysts and photoelectrocatalysts. In this study, a plasmonic Ag nanoparticles decorated CoFe2O4@TiO2 heteronanostructures have been successfully designed to fabricate a high-performing photoelectrode for the oxidation of pharmaceutical compounds. The developed Ag–CoFe2O4@TiO2 possessed a higher electrochemical stability and effectively harvested the UV to visible and NIR radiation in sunlight which generates the enormous photochemical reactive species that involved in the oxidation of ibuprofen in wastewater. Under direct sunlight irradiation, Ag–CoFe2O4@TiO2 achieved complete oxidation of ibuprofen in wastewater at 0.8 V vs RHE. This indicates that metallic Ag nanoparticles are involved in the charge separation and transport of charge carriers from the photoactive sites of CoFe2O4@TiO2, promoting the generation of abundant hydroxy, oxy, and superoxide radicals that actively break the bonds of ibuprofen. Additionally, oxidation agents such as urea and H2O2 were utilized to enhance the formation of superoxide ions and hydroxyl radicals, which rapidly participate in the oxidation of ibuprofen. Significantly, testing for recyclability confirmed the stability of the Ag–CoFe2O4@TiO2 photoanode, ensuring its suitability for prolonged use in photoelectrochemical advanced oxidation processes. Integrating Ag–CoFe2O4@TiO2 photoanodes into water purification systems could enhance economic feasibility, reduce energy consumption, and improve efficiency.

A Renal Clearable Nano-Assembly with Förster Resonance Energy Transfer Amplified Superoxide Radical and Heat Generation to Overcome Hypoxia Resistance in Phototherapeutics.

Given that type I photosensitizers (PSs) possess a good hypoxic tolerance, developing an innovative tactic to construct type I PSs is crucially important, but remains a challenge. Herein, we present a smart molecular design strategy based on the Förster resonance energy transfer (FRET) mechanism to develop a type I photodynamic therapy (PDT) agent with an encouraging amplification effect for accurate hypoxic tumor therapy. Of note, benefiting from the FRET effect, the obtained nanostructured type I PDT agent (NanoPcSZ) with boosted light-harvesting ability not only amplifies superoxide radical (O2 •-) production but also promotes heat generation upon near-infrared light irradiation. These features facilitate NanoPcSZ to realize excellent phototherapeutic response under both normal and hypoxic environments. As a result, both in vitro and in vivo experiments achieved a remarkable improvement in therapeutic efficacy via the combined effect of photothermal action and type I photoreaction. Notably, NanoPcSZ can be eliminated from organs (including the liver, lung, spleen, and kidney) apart from the tumor site and excreted through urine within 24 h of its systemic administration. In this way, the potential biotoxicity of drug accumulation can be avoided and the biosafety can be further enhanced.

Electron-Withdrawing Substituents Enhance the Type I PDT and NIR-II Fluorescence of BODIPY J Aggregates for Bioimaging and Cancer Therapy.

Organic dyes with simultaneously boosted near-infrared-II (NIR-II) fluorescence, type I photodynamic therapy (PDT), and photothermal therapy (PTT) in the aggregate state are still elusive due to the unclear structure-function relationship. Herein, electron-withdrawing substituents are introduced at the 5-indolyl positions of BODIPY dyes to form tight J-aggregates for enhanced NIR-II fluorescence and type I PDT/PTT. The introduction of an electron-rich julolidine group at the meso position and an electron-withdrawing substituent (-F) at the indolyl moiety can enhance intermolecular charge transfer and the hydrogen bonding effect, contributing to the efficient generation of superoxide radicals in the aggregate state. The nanoparticles of BDP-F exhibit NIR-II fluorescence at 1000 nm, good superoxide radical generation ability, and a high photothermal conversion efficiency (50.9%), which enabled NIR-II fluorescence-guided vasculature/tumor imaging and additive PDT/PTT. This work provides a strategy for constructing phototheranostic agents with enhanced NIR-II fluorescence and type I PDT/PTT for broad biomedical applications.

Advanced Nix/MoSx/MOF-2@g-C3N4 carbon nanostructures for the effective eradication of the Methylene blue dye

In this research, we investigated different hybrid photocatalysts: Ni/Mo.S2/MOF-2@g-C3N4, Mo.S2/MOF-2@g-C3N4, Ni.S2/MOF-2@g-C3N4 and Ni/Mo.S2/MOF-2. These photocatalysts were synthesized using a solvothermal method by incorporating Ni.x/Mo.Sx, the heterojunction showed improved separation of photoinduced charges due to disparity in charge transfer. This resulted in a narrower energy band gap and excellent catalytic activity in photodegradation. The Ni/Mo.S2/MOF-2@g-C3N4 heterostructure demonstrated outstanding photocatalytic efficiency, with up to 91% degradation of methylene blue (MB). This significant degradation was driven by the generation of superoxide (O2 •) and hydroxyl (•OH) radicals. The process adhered to pseudo-first-order kinetics and was effectively completed within 90 min of light exposure. Remarkably, the Ni/Mo.S2/MOF-2@g-C3N4 heterostructure displayed excellent stability, with only minimal performance degradation observed after five consecutive cycles. These results underscore the superior stability of the heterostructure. In summary, our research confirms that the Ni/Mo.S2/MOF-2@g-C3N4 heterojunction photocatalyst is a highly efficient material for the effective removal of methylene blue dye.

Manganese (III) phthalocyanine complex nanoassembly: Oxygen-Independent generation of superoxide radicals and singlet oxygen for ultrasound-augmented chemodynamic therapy

Singlet oxygen (1O2), an excellent reactive oxygen species (ROS) for tumor therapy, has garnered significant attention recently. However, its production is hindered by the low oxygen content in solid tumors characterized by hypoxia. Consequently, it is urgent to develop an O2-independent generator. In this study, we present a novel nano-assembly composed of manganese (Ⅲ) phthalocyanine complex (MnClPc) encapsulated by human serum albumin (MnClPc@HSA). MnClPc@HSA serves as a conventional sonosensitizer, facilitating the conversion of O2 to 1O2 under ultrasonic stimulation (US). Moreover, MnClPc@HSA enables the conversion of endogenous hydrogen peroxide (H2O2) within tumor to superoxide radical (·O2–) and 1O2 and further enhanced by US. This O2-independent generation of multiple ROS by MnClPc@HSA overcomes the limitations imposed by tumor hypoxia, while inducing immunogenic cell death (ICD) and enhancing the infiltration of T cells as well. When combined with conventional PD-L1 immunotherapy, this approach effectively inhibits the proliferation of distal and lung-metastatic tumors, while concurrently eliminating primary tumors in the bilateral-tumor model of 4 T1 tumor-bearing mice.

Interfacial interactions of polyoxometalate and Au0Pdδ+ alloy boosting aerobic oxidation of alcohols

It is significant to gain insights into the electronic interfacial interactions on non-reducible oxides as they can effectively improve the catalytic performance. Herein, we reported the fabrication of Au0Pdδ+ alloy (average size: 1.9 nm) co-modified with Na12[α-P2W15O56] (P2W15) nanoclusters on aluminum oxide (denoted as AuPd/P2W15-Al2O3) by deposition–precipitation and covalent immobilization strategy. The as-prepared AuPd/P2W15-Al2O3 exhibited 92 % conversion, 96 % selectivity of benzaldehyde with the reaction rate of 4.9 × 104h−1 when applied for the selective oxidation of benzyl alcohol, which was superior to AuPd/Al2O3, Au/P2W15-Al2O3 and Pd/P2W15-Al2O3 catalysts. Such excellent catalytic performance can be ascribed to the fact that: the electrons transfer from P2W15 to Au0Pdδ+ alloy resulted in the electron-rich Au0Pdδ+ alloy species, and the enhanced interfacial interactions between Au0Pdδ+ alloy and P2W15 nanoclusters facilitated activation of O2 to generate superoxide radicals •O2–. Moreover, density-functional theory (DFT) calculation confirmed that the P2W15 clusters modulated the d-band center of Au0Pdδ+ alloy and accelerated the adsorption of benzyl alcohol, O2 activation and desorption of benzaldehyde.

Short‐Term Soil Waterlogging Improves Cotton Tolerance to High Temperature by Triggering Antioxidant Defence System in Cotton Seedlings

ABSTRACTSoil waterlogging and high temperature (HT) are serious abiotic stresses that negatively affect cotton growth and yield. Yet effects of prewaterlogging to HT subsequently in cotton seedlings have not been obtained. To address this, two temperature conditions (30/20°C and 35/25°C) and two soil waterlogging levels (0 and 3 days) were established during the cotton seedling stage. Results showed that indexes of plant performance were decreased markedly under HT. Unexpectedly, plant performance for the treatment of HT combined with 3 days of soil waterlogging (HW) was better than HT treatment (specifically, increase of 7.9%, 9.0%, 10.2%, 5.4% and 4.6% in leaf area, plant height, belowground biomass, aboveground biomass and root‐to‐shoot ratio was detected). Decreases in MDA (malondialdehyde), H2O2 (hydrogen peroxide) contents and (superoxide radicals) generation rate under HW treatment were observed by 14.1%, 7.7% and 14.1%, respectively, compared with HT. Moreover, ASA (ascorbic acid) content and DHAR (dehydroascorbate reductase) activity were improved by 19.7% and 13.8% for HW treatment relative to HT, however, the opposite situation for activities of APX (ascorbate peroxidase) and GR (glutathione reductase). Besides, activities of SOD (superoxide dismutase), CAT (catalase) and POD (peroxidase) in HW treatment were increased by 16.7%, 8.3% and 18.4%, separately. Thus, we concluded that short‐term soil waterlogging improved cotton cross‐tolerance to the continued high‐HT stress by enhanced SOD, CAT, POD and DHAR activities, increased ASA content in cotton seedlings. These results were expected to provide a theoretical basis for understanding cotton's cross‐tolerance to abiotic stress.

Co–N–C anchored g-C3N4 plate enhancing surface activity for efficient visible-light photocatalytic rhodamine-B elimination and CO2 conversion

Poor light-harvesting, fast recombination of photo-induced charge carriers, and unfavorable surface adsorption remain the major issues restricting the photocatalytic activity of g-C3N4. In this study, the Co-N-C decorated g-C3N4 (Co-N-C/g-CN) plate was developed by constructing Co-N-C on the surface of g-CN plate to improve photocatalytic rhodamine-B (RhB) degradation and CO2 conversion. The as-prepared 0.5Co-N-C/g-CN plate exhibited an exceptionally high efficiency in photocatalytic RhB degradation, with a rate of 99.5 % achieved in mere 30 min. Besides, the 0.5Co-N-C/g-CN plate also demonstrated an outstanding photocatalytic CO2 conversion rate of 33.7 μmol g−1cat h−1 within 4 h, which was more than 3.4-fold that of g-CN (9.9 μmol g−1cat h−1). Experiments demonstrated that the surface-constructed Co-N-C enhanced the visible light-harvesting and the separation of photo-induced charge carriers, boosting the optical property. Moreover, the density functionalized theory (DFT) calculations verified that the Co-N-C cocatalyst optimized O2 adsorption for the generation of superoxide radicals (·O-2), accelerating the photocatalytic RhB removal. Meanwhile, the Co-N-C was advantageous for the adsorption and activation of CO2, facilitating the photocatalytic CO2 conversion. This study provides a perspective on the surface engineering of g-CN toward enhanced photocatalytic performance.

Thymoquinone as an electron transfer mediator to convert Type II photosensitizers to Type I photosensitizers

The development of Type I photosensitizers (PSs) is of great importance due to the inherent hypoxic intolerance of photodynamic therapy (PDT) in the hypoxic microenvironment. Compared to Type II PSs, Type I PSs are less reported due to the absence of a general molecular design strategy. Herein, we report that the combination of typical Type II PS and natural substrate carvacrol (CA) can significantly facilitate the Type I pathway to efficiently generate superoxide radical (O2–•). Detailed mechanism study suggests that CA is activated into thymoquinone (TQ) by local singlet oxygen generated from the PS upon light irradiation. With TQ as an efficient electron transfer mediator, it promotes the conversion of O2 to O2–• by PS via electron transfer-based Type I pathway. Notably, three classical Type II PSs are employed to demonstrate the universality of the proposed approach. The Type I PDT against S. aureus has been demonstrated under hypoxic conditions in vitro. Furthermore, this coupled photodynamic agent exhibits significant bactericidal activity with an antibacterial rate of 99.6% for the bacterial-infection female mice in the in vivo experiments. Here, we show a simple, effective, and universal method to endow traditional Type II PSs with hypoxic tolerance.

Fabrication of photo-induced molecular superoxide radical generator for highly efficient therapy against bacterial wound infection

The pressing need for highly efficient antibacterial strategies arises from the prevalence of microbial biofilm infections and the emergence of rapidly evolving antibiotic-resistant strains of pathogenic bacteria. Photodynamic therapy represents a highly efficient and compelling antibacterial approach, offering promising prospects for effective control of the development of bacterial resistance. However, the effectiveness of many photosensitizers is limited due to the reduced generation of reactive oxygen species (ROS) in hypoxic microenvironment, which commonly occur in pathological conditions such as inflammatory and bacteria-infected wounds. Herein, we designed and prepared two phenothiazine-derived photosensitizers (NB-1 and NB-2), which can effectively generate superoxide anion radicals (O2●–) through the type I process. Both photosensitizers demonstrate significant efficacy in vitro for the eradication of broad-spectrum bacteria. Moreover, NB-2 possesses distinct advantages including strong membrane binding and strong generation of O2●–, rendering it an exceptionally efficient antibacterial agent against mature biofilms. In addition, laser activated NB-2 could be applied to treat MRSA-infected wound in vivo, which offers new opportunities for potential practical applications.

Concerted Two-Proton-Coupled Electron Transfer from Piceatannol to Electrogenerated Superoxide in N,N-Dimethylformamide.

The reactivity of 4-[(E)-2-(3,5-dihydroxyphenyl)ethenyl]benzene-1,2-diol (piceatannol) toward electrochemically generated superoxide radical anion (O2 •-) was investigated using electrochemistry and in situ controlled-potential electrolytic electron spin resonance (ESR) measurements in N,N-dimethylformamide with density functional theory (DFT) calculations. The quasireversible cyclic voltammogram of dioxygen/O2 •-, modified in the presence of piceatannol, indicated that the electrogenerated O2 •- was scavenged by piceatannol via proton-coupled electron transfer. Differences in the reactivities of piceatannol and 5-[(E)-2-(4-hydroxyphenyl)ethen-1-yl]benzene-1,3-diol (trans-resveratrol) toward O2 •-, originating from the presence of the benzene-1,2-diol (catechol) moiety, were observed in the voltammograms and ESR measurements. The electrochemical and computational results show that the reaction mechanism is a concerted two-proton-coupled electron transfer (2PCET) via the catechol moiety of piceatannol. The stilbene moiety of piceatannol kinetically promotes 2PCET via its catechol moiety. These findings indicate that piceatannol is a better O2 •- scavenger than catechol and trans-resveratrol.

Electron Structure of α‐, β‐Te2MoO7 and Photocatalytic Decomposition of Antibiotics

AbstractTwo modifications of Te2MoO7 oxide have been prepared by different synthetic methods. The crystal structure and composition have been studied by X‐ray diffraction analysis and X‐ray microanalysis. The phase of α‐Te2MoO7 has been synthesized by solid‐state reaction from ammonium salts and characterized by monoclinic structure with P21/c. The β‐Te2MoO7 compound has been formed in hydrothermal conditions and has amorphous nature. The thermal behavior of β‐Te2MoO7 modification is characterized by the phase transition into α‐form, however after melting the amorphous state has restored. The electron structure has been investigated experimentally by X‐ray photoelectron spectroscopy and UV‐vis diffusion reflectance spectra and theoretically by approximation using atomic electronegativity. Despite the same composition, the band gap of β‐Te2MoO7 corresponds to visible light, whereas α‐Te2MoO7 adsorbs light in UV region. The both modifications are able to generate superoxide radicals in vacuum or air and hydroxyl radicals in water under irradiation. The HPLC‐MS analysis has shown the quite deep decomposition of dye and antibiotics by α‐Te2MoO7, whereas amorphous phase almost does not lead to any oxidation.

Insights into the Formation Mechanism of Reactive Oxygen Species in the Interface Reaction of SO2 on Hematite.

The interplay between sulfur and iron holds significant importance in their atmospheric cycle, yet a complete understanding of their coupling mechanism remains elusive. This investigation delves comprehensively into the evolution of reactive oxygen species (ROS) during the interfacial reactions involving sulfur dioxide (SO2) and iron oxides under varying relative humidity conditions. Notably, the direct activation of water by iron oxide was observed to generate a surface hydroxyl radical (•OH). In comparison, the aging of SO2 was found to markedly augment the production of •OH radicals on the surface of α-Fe2O3 under humid conditions. This augmentation was ascribed to the generation of superoxide radicals (•O2-) stemming from the activation of O2 through the Fe(II)/Fe(III) cycle and its combination with the H+ ion to produce hydrogen peroxide (H2O2) on the acidic surface. Moreover, the identification of moderate relative humidity as a pivotal factor in sustaining the surface acidity of iron oxide during SO2 aging underscores its crucial role in the coupling of iron dissolution, ROS production, and SO2 oxidation. Consequently, the interfacial reactions between SO2 and iron oxides under humid conditions are elucidated as atmospheric processes that enhance oxidation capacity rather than deplete ROS. These revelations offer novel insights into the mechanisms underlying •OH radical generation and oxidative potential within atmospheric interfacial chemistry.