Oxidative photocatalysis on membranes triggers non-canonical pyroptosis.

Intracellular membranes composing organelles of eukaryotes include membrane proteins playing crucial roles in physiological functions. However, a comprehensive understanding of the cellular responses triggered by intracellular membrane-focused oxidative stress remains elusive. Herein, we report an amphiphilic photocatalyst localised in intracellular membranes to damage membrane proteins oxidatively, resulting in non-canonical pyroptosis. Our developed photocatalysis generates hydroxyl radicals and hydrogen peroxides via water oxidation, which is accelerated under hypoxia. Single-molecule magnetic tweezers reveal that photocatalysis-induced oxidation markedly destabilised membrane protein folding. In cell environment, label-free quantification reveals that oxidative damage occurs primarily in membrane proteins related to protein quality control, thereby aggravating mitochondrial and endoplasmic reticulum stress and inducing lytic cell death. Notably, the photocatalysis activates non-canonical inflammasome caspases, resulting in gasdermin D cleavage to its pore-forming fragment and subsequent pyroptosis. These findings suggest that the oxidation of intracellular membrane proteins triggers non-canonical pyroptosis.

Free Radicals Generated in Perfluorocarbon-Water (Liquid-Liquid) Interfacial Contact Electrification and Their Application in Cancer Therapy.

Electron transfer during solid-liquid contact electrification has been demonstrated to produce reactive oxygen species (ROS) such as hydroxyl radicals (•OH) and superoxide anion radicals (•O2-). Here, we show that such a process also occurs in liquid-liquid contact electrification. By preparing perfluorocarbon nanoemulsions to construct a perfluorocarbon-water "liquid-liquid" interface, we confirmed that electrons were transferred from water to perfluorocarbon in ultrasonication-induced high-frequency liquid-liquid contact to produce •OH and •O2-. The produced ROS could be applied to ablate tumors by triggering large-scale immunogenic cell death in tumor cells, promoting dendritic cell maturation and macrophage polarization, ultimately activating T cell-mediated antitumor immune response. Importantly, the raw material for producing •OH is water, so the tumor therapy is not limited by the endogenous substances (O2, H2O2, etc.) in the tumor microenvironment. This work provides new perspectives for elucidating the mechanism of generation of free radicals in liquid-liquid contact and provides an excellent tumor therapeutic modality.

A ROS storm generating nanocomposite for enhanced chemodynamic therapy through H2O2 self-supply, GSH depletion and calcium overload.

Catalytic generation of toxic hydroxyl radicals (˙OH) from hydrogen peroxide (H2O2) is an effective strategy for tumor treatment in chemodynamic therapy (CDT). However, the intrinsic features of the microenvironment in solid tumors, characterized by limited H2O2 and overexpressed glutathione (GSH), severely impede the accumulation of intracellular ˙OH, posing significant challenges. To circumvent these critical issues, in this work, a CaO2-based multifunctional nanocomposite with a surface coating of Cu2+ and L-buthionine sulfoximine (BSO) (named CaO2@Cu-BSO) is designed for enhanced CDT. Taking advantage of the weakly acidic environment of the tumor, the nanocomposite gradually disintegrates, and the exposed CaO2 nanoparticles subsequently decompose to produce H2O2, alleviating the insufficient supply of endogenous H2O2 in the tumor microenvironment (TME). Furthermore, Cu2+ detached from the surface of CaO2 is reduced by H2O2 and GSH to Cu+ and ROS. Then, Cu+ catalyzes H2O2 to generate highly cytotoxic ˙OH and Cu2+, forming a cyclic catalysis effect for effective CDT. Meanwhile, GSH is depleted by Cu2+ ions to eliminate possible ˙OH scavenging. In addition, the decomposition of CaO2 by TME releases a large amount of free Ca2+, resulting in the accumulation and overload of Ca2+ and mitochondrial damage in tumor cells, further improving CDT efficacy and accelerating tumor apoptosis. Besides, BSO, a molecular inhibitor, decreases GSH production by blocking γ-glutamyl cysteine synthetase. Together, this strategy allows for enhanced CDT efficiency via a ROS storm generation strategy in tumor therapy. The experimental results confirm and demonstrate the satisfactory tumor inhibition effect both in vitro and in vivo.

Advanced remediation in the presence of ferrous iron and carbonate-containing water by oxygen-induced oxidation of organic contaminants.

Mechanistic investigations of an environmentally friendly and easy-to-implement oxidation method in the remediation of contaminated anoxic waters, i.e. groundwater, through the sole use of oxygen for the oxygen-induced oxidation of pollutants were the focus of this work. This was achieved by the addition of O2 under anoxic conditions in the presence of ferrous iron which initiated the ferrous oxidation and the simultaneous formation of reactive •OH radicals. The involvement of inorganic ligands such as carbonates in the activation of oxygen as part of the oxidation of Fe2+ in water was investigated, too. The formation of •OH radicals, was confirmed in two different, indirect approaches by a fluorescence-based method involving coumarin as •OH scavenger and by the determination of the oxidation products of different aromatic VOCs. In the latter case, the oxidation products of several typical aromatic groundwater contaminants such as BTEX (benzene, toluene, ethylbenzene, xylenes), indane and ibuprofen, were determined. The influence of other ligands in the absence of bicarbonate and the effect of pH were also addressed. The possibility of activation of O2 in carbonate-rich water i.e. groundwater, may also potentially contribute to oxidation of groundwater contaminants and support other primary remediation techniques.

Rice straw returning enhances cadmium activation by accelerating iron cycling thus hydroxyl radical production in paddy soils during drainage.

Straw returning is widely found elevating the bioavailability of cadmium (Cd) in paddy soils with unclear biogeochemical mechanisms. Here, a series of microcosm incubation experiments were conducted and spectroscopic and microscopic analyses were employed. The results showed that returning rice straw (RS) efficiently increased amorphous Fe and low crystalline Fe (II) to promote the production of hydroxyl radicals (OH) thus Cd availability in paddy soils during drainage. On the whole, RS increased OH and extractable Cd by 0.2-1.4 and 0.1-3.3 times, respectively. While the addition of RS effectively improved the oxidation rate of structural Fe (II) mineral (i.e., FeS) to enhance soil Cd activation (up to 38.5 %) induced by the increased OH (up to 69.2 %). Additionally, the existence of CO32- significantly increased the efficiency level on OH production and Cd activation, which was attributed to the improved reactivity of Fe (II) by CO32- in paddy soils. Conclusively, this study emphasizes risks of activating soil Cd induced by RS returning-derived OH, providing a new insight into evaluating the safety of straw recycling.

Recent Advances in Detection of Hydroxyl Radical by Responsive Fluorescence Nanoprobes.

Hydroxyl radical (•OH), a highly reactive oxygen species (ROS), is assumed as one of the most aggressive free radicals. This radical has a detrimental impact on cells as it can react with different biological substrates leading to pathophysiological disorders, including inflammation, mitochondrion dysfunction, and cancer. Quantification of this free radical in-situ plays critical roles in early diagnosis and treatment monitoring of various disorders, like macrophage polarization and tumor cell development. Luminescence analysis using responsive probes has been an emerging and reliable technique for in-situ detection of various cellular ROS, and some recently developed •OH responsive nanoprobes have confirmed the association with cancer development. This paper aims to summarize the recent advances in the characterization of •OH in living organisms using responsive nanoprobes, covering the production, the sources of •OH, and biological function, especially in the development of related diseases followed by the discussion of luminescence nanoprobes for •OH detection.

Dimethyl Sulfoxide: An Ideal Electrochemical Probe for Hydroxyl Radical Detection.

In situ and real-time determination of hydroxyl radicals (•OH) in physiological and pathological processes is a great challenge due to their ultrashort lifetime. Herein, an electrochemical method was developed by using dimethyl sulfoxide (DMSO) as a trapping probe for rapid determination of •OH in aqueous solution. When DMSO reacted with •OH, an intermediate product methane sulfinic acid (MSIA) was formed, which can be electrochemically oxidized to methanesulfonic acid (MSA) on the glassy carbon electrode (GCE), resulting in a distinct voltammetric signal that is directly proportional to the concentration of •OH. Other commonly encountered reactive oxygen species (ROS), including hypochlorite anions (ClO-), superoxide anions (O2•-), sulfate radicals (SO4•-), and singlet oxygen (1O2), have showed no interference for •OH determination. Thus, an electrochemical method was developed for the determination of •OH, which exhibits a wide linear range (0.4-5120 µM) and a low limit detection of 0.13 µM (S/N = 3) and was successfully applied for the quantification of •OH in aqueous extracts of cigarette tar (ACT). Alternatively, the same reaction mechanism is also applicable for the determination of DMSO, in which a linear range of 40-320 µM and a detection limit 13.3 µM (S/N = 3) was achieved. The method was used for the evaluation of DMSO content in cell cryopreservation medium. This work demonstrated that DMSO can serve as an electrochemical probe and has valuable application potential in radical study, biological research, and environmental monitoring.

Enhanced ·OH-Scavenging Activity of Cu-CeOx Nanozyme via Resurrecting Macrophage Nrf2 Transcriptional Activity Facilitates Diabetic Wound Healing.

Diabetic wounds are a prevalent and devastating complication of diabetes, which may impede their healing and regeneration. In diabetic wounds, excess reactive oxygen species (ROS) activate the nuclear factor kappa-B pathway, leading to transcriptional silencing of nuclear factor erythroid 2-related factor 2 (Nrf2), resulting in a vicious cycle of oxidative stress and inflammation. Conventional nanozymes have limitations in preventing the continuous production of ROS, including the most oxidizing reactive hydroxyl radical (·OH), although they can remove pre-existing ROS. Herein, a novel antioxidant nanoplatform addresses this challenge by incorporating JSH-23 into the mesoporous of cupric-doped cerium oxide nanozymes. Additionally, for rapid wound adaptability and durable tissue adhesion, a nanozyme hydrogel spray consisting of oxidized sodium alginate and methacrylate gelatin is constructed, named OG@CCJs. This platform resurrects Nrf2 transcriptional activity of macrophages in vitro, curbing the production of ROS at its source, particularly ·OH, while enabling the nanozymes to scavenge previously generated ROS. OG@CCJs significantly alleviate oxidative stress in diabetic wounds in vivo, promoting wound healing. Overall, the proposed nanozyme-hydrogel spray with enhanced ·OH-scavenging activity uses a "two-track" antioxidant strategy to rebuild the antioxidant defense barrier of macrophages. This pioneering approach highlights the tremendous potential of OG@CCJs for facilitating diabetic wound healing.

Phenolic compounds induce ferroptosis-like death by promoting hydroxyl radical generation in the Fenton reaction.

Phenolic compounds are industrially versatile chemicals, also the most ubiquitous pollutants. Recently, biosynthesis and biodegradation of phenols has attracted increasing attention, while phenols' toxicity is a major issue. Here, we evolved phloroglucinol-tolerant Escherichia coli strains via adaptive evolution, and three mutations (ΔsodB, ΔclpX and fetAB overexpression) prove of great assistance in the tolerance improvement. We discover that phloroglucinol complexes with iron and promotes the generation of hydroxyl radicals in Fenton reaction, which leads to reducing power depletion, lipid peroxidation, and ferroptosis-like cell death of E. coli. Besides phloroglucinol, various phenols can trigger ferroptosis-like death in diverse organisms, from bacteria to mammalian cells. Furthermore, repressing this ferroptosis-like death improves phloroglucinol production and phenol degradation by corresponding strains respectively, showing great application potential in microbial degradation or production of desired phenolic compounds, and phloroglucinol-induced ferroptosis suppresses tumor growth in mice, indicating phloroglucinol as a promising drug for cancer treatment.

Dissolved organic matter promoted hydroxyl radical formation and phenanthrene attenuation during oxygenation of iron-pillared montmorillonites.

The oxygenation of Fe(II)-bearing minerals for hydroxyl radicals (HO•) formation and contaminant attenuation receives increasing attentions. However, information on dissolved organic matter (DOM) with different types, concentrations, and molecular weights (MWs) in manipulating HO• formation and contaminant attenuation during mineral oxygenation remain unclear. In this study, four iron-pillared montmorillonites (IPMs) and two DOM samples [e.g., humic acids (HA) and fulvic acids (FA)] were prepared to explore the HO• formation and phenanthrene attenuation during the oxygenation of IPMs in the presence or absence of DOMs. Results showed that iron-pillared and high-temperature calcination procedures extended the interlayer domain of IPMs, which provided favorable conditions for a high HO• production from 1293 to 14537 µmol kg-1. The surface-absorbed/low crystalline Fe(Ⅱ) was the predominant Fe(Ⅱ) fractionations for HO• production, and presence of DOMs significantly enhanced the HO• production and phenanthrene attenuation. Moreover, regardless of the types and concentrations, the low MW (LMW, <1 kDa) fraction within DOM pool contributed highest to HO• production and phenanthrene attenuation, followed by the bulk and high MW (HMW-, 1 kDa∼0.45 µm) fractions, and FA exhibited more efficient effects in promoting HO• production and phenanthrene attenuation than HA. The fluorescent spectral analysis further revealed that phenolic-like fluorophores in LMW-fraction were the main substances responsible for the enhanced HO• production and phenanthrene attenuation. The results deepen our understandings toward the behaviors and fate of aquatic HO• and contaminants, and also provide technical guidance for the remediation of contaminated environments.

Effects of dietary methionine supplementation on the growth performance, immune responses, antioxidant capacity, and subsequent development of layer chicks.

Deficiencies or excesses of dietary amino acids, and especially of methionine (Met), in laying hens can lead to abnormal protein anabolism and oxidative stress, which affect methylation and cause cellular dysfunction. This study investigated the effects of dietary methionine (Met) levels on growth performance, metabolism, immune response, antioxidant capacity, and the subsequent development of laying hens. A total of 384 healthy 1-day-old Hyline Grey chicks of similar body weight were randomly allocated to be fed diets containing 0.31%, 0.38%, 0.43% (control group), or 0.54% Met for 6 wk, with 6 replicates of 16 chicks in each. The growth performance of the chicks was then followed until 20 wk old. The results showed dietary supplementation with 0.43% or 0.54% Met significantly increased their mean daily body weight gain, final weight, and Met intake. However, the feed:gain (F/G) decreased linearly with increasing Met supplementation, from 0.31 to 0.54% Met. Met supplementation increased the serum albumin, IgM, and total glutathione concentrations of 14-day-old chicks. In contrast, the serum alkaline phosphatase activity and hydroxyl radical concentration tended to decrease with increasing Met supplementation. In addition, the highest serum concentrations of IL-10, T-SOD, and GSH-PX were in the 0.54% Met-fed group. At 42 d of age, the serum ALB, IL-10, T-SOD, GSH-PX, T-AOC, and T-GSH were correlated with dietary Met levels. Finally, Met supplementation reduced the serum concentrations of ALP, IL-1ß, IgA, IgG, hydrogen peroxide, and hydroxyl radicals. Thus, the inclusion of 0.43% or 0.54% Met in the diet helps chicks achieve superior performance during the brooding period and subsequently. In conclusion, Met doses of 0.43 to 0.54% could enhance the growth performance, protein utilization efficiency, antioxidant capacity, and immune responses of layer chicks, and to promote more desirable subsequent development during the brooding period.

Surface disinfection of wheat kernels using gas phase hydroxyl-radical processes: Effect on germination characteristics, microbial load, and functional properties.

Wheat kernels harbor a diverse microflora that can negatively affect the suitability of the grains for further processing. To reduce surface microflora, a kernel disinfection method is required that does not affect grain functionality. Three different versions of gas phase hydroxyl-radical processes were compared with the common method for grain disinfection, that is, a bleach treatment. The gas phase hydroxyl-radicals are generated by the UV-C mediated degradation of hydrogen peroxide and/or ozone in a near water-free process. It was found that treating kernels with a bleach solution could reduce total aerobic count (TAC) and fungal count to below the level of enumeration. In comparison, the gas phase hydroxyl-radical treatment, that is, H2 O2 -UV-ozone treatment, could support a 1.3 log count reduction (LCR) in TAC and a 1.1 LCR in fungal count. The microbial load reduction for the wholemeal samples was less pronounced as endophytic microorganisms were less affected by all treatments, hinting at a limited penetration depth of the treatments. Despite reducing the microbial load on the kernel surface through the bleach and H2 O2 -UV-ozone treatments, none of these treatments resulted in a reduced microbial count on grains that underwent sprouting after the treatments. No negative effect on germination power or development of the seedling was observed for any of the treatments. The gluten aggregation behavior and xylanase activity of the wholemeal also remained unchanged after the gas phase hydroxyl-radical treatments. Our findings suggest that UV-H2 O2 -ozone treatment shows promise for dry-kernel disinfection, but further optimization of the processing parameters is required.

A novel iron sulfide phase with remarkable hydroxyl radical generation capability for contaminants degradation.

The hydroxyl radical (·OH) stands as one of the most potent oxidizing agents, capable of engaging in non-selective and instantaneous reactions with contaminants in water. Herein, we present a novel iron sulfide phase (S-FeS) characterized by an unprecedented structure, accompanied by its remarkable hydroxyl radical generation capability and contaminant degradation efficiency surpassing that of the conventional metastable iron sulfide phase, namely, the Mackinawite (FeS). In comparison to FeS, S-FeS exhibits enhanced degradation kinetics and higher efficacy in the removal of methylene blue, ciprofloxacin, and trivalent arsenic. Utilizing density functional theory (DFT) calculations, we postulate the mechanism for the exceptional contaminant degradation performance of S-FeS to be attributed to the increased exposure of the highly reactive (110) crystal facets. This research uncovers a new metastable phase that expands the polymorphisms within the iron sulfide family and showcases its capability for driving the oxygen reduction reaction.

New Barrier Role of Iron Plaque: Producing Interfacial Hydroxyl Radicals to Degrade Rhizosphere Pollutants.

Iron plaque, as a natural barrier between rice and soil, can reduce the accumulation of pollutants in rice by adsorption, contributing to the safe production of rice in contaminated soil. In this study, we unveiled a new role of iron plaque, i.e., producing hydroxyl radicals (·OH) by activating root-secreted oxygen to degrade pollutants. The ·OH was produced on the iron plaque surface and then diffused to the interfacial layer between the surface and the rhizosphere environment. The iron plaque activated oxygen via a successive three-electron transfer to produce ·OH, involving superoxide and hydrogen peroxide as the intermediates. The structural Fe(II) in iron plaque played a dominant role in activating oxygen rather than the adsorbed Fe(II), since the structural Fe(II) was thermodynamically more favorable for oxygen activation. The oxygen vacancies accompanied by the structural Fe(II) played an important role in oxygen activation to produce ·OH. The interfacial ·OH selectively degraded rhizosphere pollutants that could be adsorbed onto the iron plaque and was less affected by the rhizosphere environments than the free ·OH. This study uncovered the oxidative role of iron plaque mediated by its produced ·OH, reshaping our understanding of the role of iron plaque as a barrier for rice.

GSH/pH Dual Activatable Cross-linked and Fluorinated PEI for Cancer Gene Therapy Through Endogenous Iron De-Hijacking and in Situ ROS Amplification.

Ferroptosis-related cancer therapy is limited by insufficient Fe2+ /Fe3+ redox pair and hydrogen peroxide (H2 O2 ) for producing lethal hydroxyl radicals (·OH). Although exogenous iron or ROS-producing drugs can enhance ferroptosis, exploiting endogenous iron (labile iron pool, LIP) stored in ferritin and promoting ROS generation may be safer. Herein, a metal/drug-free nanomedicine is developed for responsive LIP release and H2 O2 generation on the mitochondria membranes, amplifying hydroxyl radical production to enhance ferroptosis-mediated antitumor effects. A glutathione(GSH)/pH dual activatable fluorinated and cross-linked polyethyleneimine (PEI) with dialdehyde polyethylene glycol layer nanocomplex loaded with MTS-KR-SOD (Mitochondria-targeting-sequence-KillerRed-Superoxide Dismutase) and CRISPR/Cas9-CA IX (Carbonic anhydrase IX (CA IX)) plasmids (FP@MC) are developed for enhanced ferroptosis through endogenous iron de-hijacking and in situ ROS amplification. Two plasmids are constructed to knockdown CA IX and translate KillerRed-SOD recombinant protein specifically on mitochondria membranes, respectively. The CA IX knockdown acidifies the intracellular environment, leading the release of LIP from ferritin as a "flare" to initiate endogenous chemodynamic therapy. Meanwhile, MTS-KR-SOD generates H2 O2 when irradiated by a 590 nm laser to assist chemodynamic therapy, leading to ROS amplification for mitochondria damage and lipid peroxide accumulation. The combined therapeutic effects aggravate cancer ferroptosis and suppress tumor growth, providing a new paradigm for amplifying ROS and iron ions to promote ferroptosis-related cancer therapy.

Degradation of Ampicillin with antibiotic activity removal using persulfate and submersible UVC LED: Kinetics, mechanism, electrical energy and cost analysis.

Effective water treatment to remove antibiotics and its activity from contaminated water is urgently needed to prevent antibiotic-resistant bacteria (ARB) emergence. In this study, we investigated degradation of Ampicillin (AMP), an extensively used ß-lactam antibiotic, using submersible Ultraviolet C Light Emitting Diode (λmax = 276 nm) irradiation source, and Persulfate (UVC LED/PS system). Pseudo first order rate constant (kobs) for degradation of AMP (1 ppm) by UVC LED/PS system was determined to be 0.5133 min-1 (PS = 0.2 mM). kobs value at pH 2.5 (0.7259 min-1) was found to be higher than pH 6.5 (0.5133 min-1) and pH 12 (0.1745 min-1). kobs value for degradation of AMP in deionized water spiked with inorganic anions (Cl-=0.5369 min-1,SO42-=0.4545 min-1, NO3-=0.1526 min-1, HCO3-=0.0226 min-1), in real tap water (0.1182 min-1) and simulated ground water (0.0372 min-1) were presented. Radical scavenging experiment reveal involvement of sulfate radical anion and hydroxyl radical in UVC LED/PS system. EPR analysis confirms the generation of sulfate radical anion and hydroxyl radical. Importantly, 74% reduction of total organic carbon (TOC) occurred within 60 min of AMP treatment by UVC LED/PS system. Seven degradation by-products were identified by high resolution mass spectrometry, and degradation pathways were proposed. Antibacterial activity of AMP towards Bacillus subtilis and Staphylococcus aureus was completely removed after UVC LED/PS treatment. ECOSAR model predicted no very toxic degradation by-products generation by UVC LED/PS system. Electrical Energy per order (EEo) and cost of UVC LED/PS system were determined to be 0.9351 kW/m3/order and ₹ 7.91/m3 ($ 0.095/m3 or € 0.087/m3), respectively. Overall, this study highlights, UVC LED/PS system as energy efficient, low-cost, and its potential to emerge as sulfate radical anion based advanced oxidation process (AOP) to treat water with antibiotics.

Polymerized PEI-modified lignin polyphenolic materials by acid hydrolysis-phase separation for removal of Cr (VI) from industrial wastewater.

Cr (VI) accumulates in an aqueous environment and exhibits huge harm to human health and the ecological system. Developed lignin biomass materials are complicated to prepare and have limited properties, and advances in lignin phenolic modification are lacking. Herein, an aminated poplar lignin-pyrogallol (PLP-PEI) with a simple design and adjustable phenolic hydroxyl content was developed using the acid hydrolysis-phase separation (AH-PS) method, and modified by the atom transfer radical polymerization (ATRP) strategy. Through diverse characterization analysis, the structural changes of PLP-PEI in the step-by-step synthesis process were monitored. An effective biomass capture system (Bio-Cap) was shown via systematically investigating the adsorption behaviors of Cr (VI) on PLP-PEI under various environmental conditions. Benefiting from introducing phenolic hydroxyl and amino groups, PLP-PEI demonstrated efficient adsorption capacity (598.80 mg/g for Cr (VI)). Additionally, the material also exhibited advantages, including monomeric chemisorption properties, strong reduction capability, and stable regeneration properties. Multiple driving forces were involved in the capture and removal process of Cr (VI), including complexation and electrostatic interaction. The low-cost natural biomass resources supported the industrial-scale synthesis and practical application of advanced aminated lignin polyphenol material, which showed outstanding advantages and enormous potential in the field of water environmental restoration.

Ultrasound-Driven Non-Metallic Fenton-Active Center Construction for Extensive Chemodynamic Therapy.

Chemodynamic therapy (CDT) is an emerging tumor microenvironment-responsive cancer therapeutic strategy based on Fenton/Fenton-like reactions. However, the effectiveness of CDT is subject to the slow kinetic rate and non-homogeneous distribution of H2 O2 . In this study, a conceptual non-metallic "Fenton-active" center construction strategy is proposed to enhance CDT efficiency using Bi0.44 Ba0.06 Na0.5 TiO2.97 (BNBT-6) nanocrystals. The separated charge carriers under a piezoelectric-induced electric field synchronize the oxidation of H2 O and reduction of H2 O2 , which consequently increases hydroxyl radical (·OH) yield even under low H2 O2 levels. Moreover, acceptor doping induces electron-rich oxygen vacancies to facilitate the dissociation of H2 O2 and H2 O and further promote ·OH generation. In vitro and in vivo experiments demonstrate that BNBT-6 induces extensive intracellular oxidative stress and enhances cell-killing efficiency by activating necroptosis in addition to the conventional apoptotic pathway. This study proposes a novel design approach for nanomaterials used in CDT and presents a new treatment strategy for apoptosis-resistant tumors.

Theoretical investigation on the mechanism and kinetics of the OH•‒initiated atmospheric degradation of p-chloroaniline: Addition of ∑g-3O2 and isomerization of peroxy radicals.

Atmospheric oxidation of the p-chloroaniline-OH• adduct [C6H4ClNH2-OH]• (AD-C2) by ∑g-3O2 and internal isomerization processes of peroxy radical [C6H4ClNH2-OH]•-O2 are theoretically investigated at the M06-2X/aug-cc-pVTZ and CBS-QB3//M06-2X/aug-cc-pVTZ level of theories. Potential energy surfaces (PESs) for the most efficient pathways indicated that the oxidation process begins via the complexation of individual reactants in syn mode forming PRCy-iOO-syn (y = 2,5) in an exothermic and endogenic step. The syn mode addition is favored over the anti one due to the formation of internal hydrogen bond between the hydroxyl and peroxy groups. Formation of new C5-OO bond in PRCy-iOO-syn complex is an unimolecular process which is exothermic and exoergic. This pathway is predominated over other internal conversions due to the presence of stronger intramolecular hydrogen bond. Cyclization of the produced [C6H4ClNH2-OH]•-O2 peroxy radical AD-C2-5OO-syn into the bicyclic peroxy radical AD-C2-5,6OO-syn is the last step which is strongly endothermic and endogenic. The rate coefficients are calculated by means of the RRKM theory over the temperature range 250-350 K and at a pressure range of 0.1 bar to the high-pressure limit. The RRKM rate coefficients at the M06-2X/aug-cc-pVTZ level for the first bimolecular and last unimolecular steps are in order of 10-16 cm3 molecule-1 s-1 and 10-7 s-1, respectively, while the obtained rate coefficients at the CBS-QB3//M06-2X/aug-cc-pVTZ are overestimated about two order of magnitude.