Increased Hydroxyl Radical Research Articles

NIR-II triggered Cu(I) phosphide for chemodynamic and photothermal periodontitis treatment: Efficient reduction of bacterial co-aggregation

The synergy between chemodynamic therapy (CDT) and photothermal therapy (PTT) offers a promising antimicrobial strategy for periodontitis, yet faces challenges like complex material structure and limited NIR-I light penetration. Additionally, low endogenous H2O2 levels in biofilm and a focus on bacterial eradication over colonization prevention limit current treatments. To address these issues, we newly introduce a single-material system (Cu3P@PAH@Lox) that integrates dual functionalities to synergistically enhance antimicrobial effects and significantly reduce pathogen co-aggregation. This system utilizes PTT to increase local temperature, boosting •OH production in CDT while downregulating heat shock proteins to enhance PTT efficacy, forming a self-reinforcing feedback loop. Lactate oxidase (Lox) is employed to convert lactate—a metabolite in periodontal biofilm—into H2O2, further amplifying CDT's potential. In vitro Cu3P@PAH@Lox demonstrates a remarkable synergistic effect against dual-species biofilms by more than 2-log reduction of colony-forming unit. Moreover, Cu3P@PAH@Lox exhibits outstanding synergistic antibacterial performances to alleviate inflammation and destruction of tissue in vivo periodontitis model. Furthermore, the mechanism of pathogen co-aggregation disruption by PTT is verified via the Cbe-Ltp1-Ptk1-fimA signaling pathway. This single-material multimodal system we have herein demonstrated for the first time marks a significant advancement in periodontitis treatment, eradicating microbes and preventing bacterial colonization, offering a path to comprehensive periodontal care. Statement of significanceThe synergy between chemodynamic therapy (CDT) and photothermal therapy (PTT) has been considered a promising therapy for periodontitis. Yet, facing challenges, the complex material structure, limited NIR-I light penetration, low endogenous H2O2 level in biofilm, and a focus on bacterial eradication over colonization prevention are still insufficient. This study pioneers a unique, single-material system (Cu3P@PAH@Lox) that synergistically enhances antimicrobial effects and substantially curtails pathogen co-aggregation, advancing periodontitis therapy. By exploiting PTT to elevate local temperatures, thereby increasing hydroxyl radical production in CDT and concurrently suppressing heat shock proteins, the system establishes a potent, self-enhancing loop. Furthermore, lactate oxidase is innovatively utilized to convert lactate from periodontal biofilm into hydrogen peroxide, augmenting the efficacy of CDT. The introduction of Cu3P@PAH@Lox is poised to revolutionize periodontitis treatment, eliminating microbes and impeding bacterial colonization, thereby charting a course for comprehensive periodontal management.

Bio-inspired Cu2O cathode for O2 capturing and oxidation boosting in electro-Fenton for sulfathiazole decay

A hydrophobic Cu2O cathode (CuxO-L) was designed to solve the challenge of low oxidation ability in electro-Fenton (EF) for treating emerging pollutants. This fabrication process involved forming Cu(OH)2 nanorods by oxidizing copper foam (Cu-F) with (NH4)2S2O8, followed by coating them with glucose via hydrothermal treatment. Finally, a self-assembled monolayer of 1-octadecanethiol was introduced to create a low-surface-energy, functionalized CuxO-L cathode. Results exhibited an approximately 7.9-fold increase in hydroxyl radical (·OH) generation compared to the initial Cu-F. This enhancement was attributed to two key factors: (Ⅰ) the superior O2-capturing ability of CuxO-L cathode, which led to high H2O2 production due to a 2 nm thick hydrophobic gas layer facilitated O2-capturing; (Ⅱ) a relative high concentration of Cu+ at the CuxO-L cathode promoted the activation of H2O2 into·OH. In addition, the performance of EF with the CuxO-L cathode using sulfathiazole (STZ) as a model pollutant was evaluated. This study offers valuable insights into the design of O2-capturing cathodes in EF processes, particularly for treating emerging organic pollutants.

Catalytic activity of violet phosphorus-based nanosystems and the role of metabolites in tumor therapy.

Although nanocatalytic medicine has demonstrated its advantages in tumor therapy, the outcomes heavily relie on substrate concentration and the metabolic pathways are still indistinct. We discover that violet phosphorus quantum dots (VPQDs) can catalyze the production of reactive oxygen species(ROS) without requiring external stimuli and the catalytic substrates are confirmed to be oxygen (O2) and hydrogen peroxide (H2O2) through the computational simulation and experiments. Considering the short of O2 and H2O2 at the tumor site, we utilize calcium peroxide (CaO2) to supply catalytic substrates for VPQDs and construct nanoparticles together with them, named VPCaNPs. VPCaNPs can induce oxidative stress in tumor cells, particularly characterized by a significant increase in hydroxyl radicals and superoxide radicals, which cause substantial damage to the structure and function of cells, ultimately leading to cell apoptosis. Intriguingly, O2 provided by CaO2 can degrade VPQDs slowly, and the degradation product, phosphate, as well as CaO2-generated calcium ions, can promote tumor calcification. Antitumor immune activation and less metastasis are also observed in VPCaNPs administrated animals. In conclusion, our study unveils the anti-tumor activity of VPQDs as catalysts for generating cytotoxic ROS and the degradation products can promote tumor calcification, providing a promising strategy for treating tumors.

High-entropy oxide (CeGdHfPrZr)O2 nanoparticles as reusable photocatalyst for wastewater remediation

High-entropy materials (HEM) play a significant role in current scientific research and are characterized by their complexity, which makes them the next generation nanomaterials. The present study investigates the synthesis of (CeGdHfPrZr)O2 high-entropy oxide nanoparticles using a hydrothermal technique. Various characterization techniques, such as X-ray diffraction (XRD), and scanning electron microscopy (SEM) were used to investigate the structural properties, while UV-visible spectroscopy was used to investigate the optical properties. The results indicate the formation of a single-phase cubic fluorite high-entropy oxide system with a mean crystallite size of 5.4 nm. The optical bandgap of (CeGdHfPrZr)O2 nanoparticles is found to be 2.01 eV. The photocatalytic activity of the synthesized oxide nanoparticles was assessed using methylene blue (MB) dye as a model pollutant. In the current study, we examined and discussed the effect of various photocatalytic parameters on the degradation of MB dye. The results showed that the (CeGdHfPrZr)O2 nanoparticles had high photocatalytic activity and were found to be dependent on various parameters. A higher photocatalyst concentration impedes the degradation kinetics and, as a result, limits photon penetration into the reaction solution. Similarly, increased hydroxyl radical generation at a basic pH improved MB dye degradation. In addition, based on the band positions and radical scavenging study, hydroxyl radicals are responsible for the degradation of dye. (CeGdHfPrZr)O2 nanoparticles can be used as a promising catalyst for the photocatalytic degradation of organic pollutants.

Efficient and low-energy consumption degradation of bisphenol A in aqueous solutions and its density functional theory calculation

An advanced Fenton technique using urea peroxide (UHP) as an oxidant was studied for the degradation of bisphenol A (BPA) in aqueous solution. Compared to the H2O2/Fe(II) system, the UHP/Fe(II) system performs noticeably better in terms of degradation and requires less catalyst. The mechanism by which UHP exhibits unique and remarkable properties has been elucidated at the molecular level (bond order, AIM analysis, ELF, Spin Population number, electron difference density maps) by density functional theory (DFT) calculations. The ELF and the electron density difference revealed that UHP created an intermediate coordination compound with six-coordinated iron (II), facilitating electron transfer and the disruption of O-O bonds because of the feeble O-O strength, leading to an increase in hydroxyl radicals. Consequently, UHP increases the rate of electron usage and targeting efficiency, which accelerates the breakdown of BPA. targeting efficiency, which accelerates the breakdown of BPA. Based on the intermediates determined by LC-MS/MS, the possible degradation pathway of BPA in the UHP/Fe(II) system were proposed, which was verified to be a lower energy consumption pathway by calculating the reaction energy barriers. It is expected to be an advanced Fenton technology with practical engineering applications potential, due to the advantages of wider pH window, lower energy consumption and higher electron utilization.

Integrated drug delivery system loading ROS-generating antitumor drugs for signal-amplified photoacoustic imaging and multimodal tumor therapy

The usefulness of antitumor drugs that produce reactive oxygen species (ROS) in accurate tumor diagnosis and treatment has been underestimated. Here, β-Lapachone (Lapa, antitumor drugs), 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS, precursor photoacoustic agents) and 2, 2′-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride (AIPH, free radical initiators) were successfully loaded into zeolitic imidazolate framework (ZIF) in situ by a one-pot method and named Lapa/ABTS/AIPH@ZIF-67 nanoparticles (LBIZ NPs). After entering the tumor cell, the ZIF structure of LBIZ NPs is disrupted in the acidic tumor microenvironment, which results in the release of Co2+ and drugs. In one hand, Lapa and Co2+ together increased hydroxyl radicals (•OH) levels to achieve Enhanced-Chemodynamic therapy (ECDT). As the amount of •OH went up, the amount of ABTS•+, the oxidation product of ABTS, would also increase, thus increasing the sensitivity and contrast of photoacoustic imaging. In the other hand, the photothermal effect produced by ABTS•+ induces AIPH to crack and release alkyl radicals (•R) to achieve thermodynamic therapy. The LBIZ NPs achieved more effective tumor treatments by fully utilizing light and heat energy. Hence, this integrated drug delivery system is able to achieve signal-amplified photoacoustic imaging and Enhanced-Chemodynamic/Photothermal/Thermodynamic trimodal combination therapy. This work provides a new insight into the application of ROS-generating antitumor drugs to precise imaging of tumors.

The deletion of ppr2 interferes iron sensing and leads to oxidative stress response in Schizosaccharomyces pombe

Pentatricopeptide repeat proteins are involved in mitochondrial both transcriptional and posttranscriptional regulation. Schizosaccharomyces pombe Ppr2 is a general mitochondrial translation factor that plays a critical role in the synthesis of all mitochondrial DNA-encoded oxidative phosphorylation subunits, which are essential for mitochondrial respiration. Our previous analysis showed that ppr2 deletion resulted in increased expression of iron uptake genes and caused ferroptosis-like cell death in S. pombe. In the present work, we showed that deletion of ppr2 reduced viability on glycerol- and galactose-containing media.Php4 is a transcription repressor that regulates iron homeostasis in fission yeast. We found that in the ppr2 deletion strain, Php4 was constitutively active and accumulated in the nucleus in the stationary phase. We also found that deletion of ppr2 decreased the ferroptosis-related protein Gpx1 in the mitochondria. Overexpression of Gpx1 improves the viability of Δppr2 cells. We showed that the deletion of ppr2 increased the production of ROS, downregulated heme synthesis and iron-sulfur cluster proteins, and induced stress proteins. Finally, we observed the nuclear accumulation of Pap1-GFP and Sty1-GFP, suggesting that Sty1 and Pap1 in response to cellular stress in the ppr2 deletion strain. These results suggest thatppr2 deletion may cause mitochondrial dysfunction, which is likely to lead to iron-sensing defect and iron starvation response, resulting in perturbation of iron homeostasis and increased hydroxyl radical production. The increased hydroxyl radical production triggers cellular responses in theppr2 deletion strain.

Adsorption behavior of lead, cadmium, and arsenic on manganese-modified biochar: competition and promotion.

Biochar adsorption of heavy metals has been a research hotspot, yet there has been limited reports on the effect of heavy metal interactions on adsorption efficiency in complex systems. In this study, the adsorbent was prepared by pyrolysis of rice straw loaded with manganese (BC-Mn). The interactions of Pb, Cd and As adsorption on BC-Mn were systematically studied. The results of the adsorption isotherms for the binary metal system revealed a competitive adsorption between Pb and Cd, resulting in decreased Pb (from 214.38mg/g to 148.20mg/g) and Cd (from 165.73mg/g to 92.11mg/g). A notable promotion occurred between As and Cd, showing an increase from 234.93mg/g to 305.00mg/g for As and 165.73mg/g to 313.94mg/g for Cd. In the ternary metal system, Pb inhibition did not counteract the promotion of Cd and As. Furthermore, the Langmuir isotherm effectively described BC-Mn's adsorption process in monometallic, binary, and ternary metal systems (R2 > 0.9294). Zeta and FTIR analyses revealed simultaneous competition between Pb and Cd for adsorption on BC-Mn's -OH sites. XPS analysis revealed that As adsorption by BC-Mn facilitated the conversion of MnO2 and MnO to MnOOH, resulting in increased hydroxyl radical production on BC-Mn's surface. Simultaneously, Cd combined with the adsorbed As to form ternary Cd-As-Mn complexes, which expedited the removal of Cd. These results help to provide theoretical support as well as technical support for the treatment of Pb-Cd-As contaminated wastewater.

Simultaneous degradation and rejection of PPCPs from wastewater in a 3DEO-FO-RO process

This study established a novel three-dimensional electrochemical oxidation coupled with forward osmosis and reverse osmosis (3DEO-FO-RO) system with the purpose to achieve simultaneous degradation and rejection of pharmaceuticals and personal care products (PPCPs) in wastewater. 18 frequently detected PPCPs were selected as the target pollutants to prepare the synthetic wastewater with a concentration of 200 μg/L for each pollutant. Ti/IrO2–Ta2O5–SnO2 mesh anode, titanium mesh cathode and Sn–Sb–Bi/γ-Al2O3 particles electrodes were integrated in the 3DEO-FO reactor. Experimental results demonstrated that degradation efficiency exceeding 98.5 % and rejection exceeding 99.4 % for each PPCP were achieved simultaneously in the 3DEO-FO-RO processes at a current density of 1 mA/cm2 after 8 h treatment. Despite variations in applied current density, the 3DEO-FO-RO processes exhibited superior PPCPs removal efficiencies, particularly for refractory compounds, compared to the 2DEO-FO-RO processes. Increased hydroxyl radical (·OH) generation in the 3D reactor was considered to be responsible for the excellent performance. Furthermore, results derived from ultraviolet (UV) absorption spectra and fluorescence excitation-emission matrix (EEM) spectra provided additional validation for the effective removal of PPCPs in the 3DEO-FO-RO processes, along with evidence indicating the decomposition of PPCPs into smaller constituents. Ultimately, the 3DEO-FO-RO process demonstrated its capacity in removing PPCPs from actual secondary effluent from a wastewater treatment plant. This integrated system coupling 3D EO with FO-RO membranes can provide an efficient approach for simultaneous degradation and rejection of trace contaminants for wastewater reuse.

Study on the mechanism of rapid degradation of Rhodamine B with Fe/Cu@antimony tailing nano catalytic particle electrode in a three dimensional electrochemical reactor

A novel particle electrode based on antimony tailings microspheres was successfully constructed by ultrasonic immersion calcination method, and the degradation of RhB was studied in a three-dimensional electrochemical reactor (3DER). It was characterized by XRD, SEM, EDS, XPS, cyclic voltammetry and linear sweep voltammetry. When the pH value is 5.00, the dosage of Fe/Cu@antimony tailing is 1.50 g/L, the initial concentration is 100 mg/L, and the current density is 20 mA/cm2, the degradation efficiency is the best (99.40% for RhB and 98.81% for TOC) within 15 min. The results show that in the three-dimensional electrochemical oxidation system, electrochemical oxidation and electro Fenton oxidation occur at the same time to cause the increase of hydroxyl radicals. According to LC-MS analysis and EPR characterization, it can be found that the main degradation mechanism of RhB is that hydroxyl radicals continuously attack RhB, and realize rapid degradation of RhB through deethylation, deamination, dealkylation, decarboxylation, chromophore splitting, ring opening and mineralization. Fe/Cu@antimony tailing particles are both electrodes for electrochemical oxidation and catalysts for Fenton oxidation. The degradation effect of RhB remained at 94% after 6 cycles, and the leaching rates of Fe and Cu are only 1.20% and 0.79%, indicating that Fe/Cu@AT had significant stability. This work provides a new insight into the establishment of an efficient and stable three-dimensional electrocatalytic particle electrode.

Oxidative and Photochemical Processes for Soft Drink–Industry Wastewater Treatment

Soft drinks–industry wastewater (SDIW) contains high concentrations of sugar (420–487 mg/L) and sodium (320–397 mg/L), has high pH (∼9), and contains biorefractory pollutants. Therefore, rapid and effective techniques are required for its treatment. In the present study, SDIW was subjected to microwave (MW) photocatalysis (PC) using electrodeless discharge lamps, and the outcomes were compared with other oxidative and photochemical advanced oxidation processes, including oxidation, MW oxidation (MWO), and ultraviolet–titanium dioxide PC, in terms of the removal efficiency of organics based on chemical oxygen demand (COD), total phosphate (TP), and total nitrogen (TN). The mineralization of organics was ∼3.5 times higher in the MWPC and MWO systems compared to the oxidation and PC systems. The COD removal efficiency after 60 min using the oxidation, PC, MWO, and MWPC systems was 22.7%, 25.41%, 79.36%, and 87.3%, respectively. Direct photolysis using UV (using 486 kJ/mole of energy) and photocatalytic degradation using increased hydroxyl radicals in the presence of MWs was the primary degradation mechanism in the MWPC system. The TP removal efficiency in the oxidation, PC, MWO, and MWPC systems was 15%, 40%, 50%, and 60%, respectively. The respective TN removal efficiencies for the four systems were 40%, 58%, 82%, and 85%. The main mechanism for organics, TP, and TN removal in the MWPC system involved the direct disruption of the chemical bonds of the organic molecules, photocatalytic phosphate reduction, and breaking of the primary amine bond in the organic nitrogen using the high-energy plasma and hotspots that formed in the MW-based systems. The electrical energy consumed by the systems [electrical energy per order (EEO)] occurred in the order PC > MWO > MWPC, with respective values of 14,614, 6,919, and 4,526 Rs/kg COD removal.

Pre-exposure of peracetic acid enhances its subsequent combination with ultraviolet for the inactivation of fungal spores: Efficiency, mechanisms, and implications

Waterborne fungi pose a potential threat to water supply safety due to their high resistance to disinfectants. Peracetic acid, as a promising alternative disinfectant to chlorine, has attracted increasing attention in water treatment. In this study, the inactivation of two dominant fungal species (Aspergillus niger and Aspergillus flavus) by sequential application of peracetic acid and ultraviolet (PAA-UV/PAA) was reported for the first time. Results revealed that the pre-exposure of PAA could facilitate the subsequent process of UV/PAA combination and shorten the lag phase in fungi inactivation. After 10 min of PAA pre-exposure, PAA-UV/PAA achieved 3.03 and 2.40 log inactivation of Aspergillus niger and Aspergillus flavus, which were 2- and 4.3-fold higher than that of direct UV/PAA under the same UV and PAA doses. PAA-UV/PAA disinfection also exhibited a stronger regrowth inhibition for incompletely inactivated fungal spores than direct UV/PAA. The increase of pH (5.0–9.0) and humic acid concentration (1.0–5.0 mg L − 1) showed an inhibitory effect on PAA-UV/PAA inactivation, but PAA-UV/PAA was more adaptable in a wide pH range and the presence of humic acid compared to direct UV/PAA. The more severe cell membrane damage and higher reactive oxygen species level in PAA-UV/PAA were evidenced for the first time by flow cytometry. The increased hydroxyl radical generation and higher synergism were primarily responsible for inactivation improvement. This study enhances the further understanding of the PAA-UV/PAA process, and the findings are expected to promote the development of PAA as a promising disinfectant for effective fungi control.

Reuse of secondary aluminum ash: Study on removal of fluoride from industrial wastewater by mesoporous alumina modified with citric acid

Longitudinal loading of citric acid as modifier onto the surface of other supports as highly efficient fluoride removing adsorbents has received extensive attention. But the loading of acid into mesoporous alumina synthesized using industrial solid waste secondary aluminum ash as raw material is rarely reported. In this study, MA was prepared by secondary aluminum ash reuse to industrial solid waste, and the MA was modified with citric acid for fluoride removal. The structural properties of this adsorbent were characterized by N 2 adsorption–desorption isotherm, XRD, FTIR spectroscopy. Meanwhile, the adsorption conditions, such as contact time, initial concentration and pH, were examined to evaluate the effect of fluoride adsorption. The adsorption properties are stable under acidic conditions. Chemisorption is a rate determining step because it complies with the Langmuir model and the pseudo second order model. The adsorption equilibrium was quickly reached in 30 min (117.98 mg g −1 ). With good cycling performance, 98.20% of the initial adsorption capacity was maintained after 5 cycles. Ion exchange between OH and fluoride is the main process of fluoride adsorption. The introduction of citric acid greatly increased the amount of -OH in the adsorbent. The extent of the influence of coexisting anions on fluoride adsorption is most pronounced for PO 4 3 − and CO 3 2 − . The results of high fluoride containing industrial wastewater treatment show that citric acid modified MA can solve the environmental pollution problem of industrial solid waste secondary aluminum ash on one hand, and at the same time provide new ideas for fluoride adsorbents. • Synthesizing mesoporous alumina with secondary aluminum ash for the first time. • Modification with citric acid increased hydroxyl radical on the surface of the material. • The removal efficiency remains above 98.20% after 5 cycles. • The maximum adsorption capacity for fluoride ions was 117.98 mg g −1 .

Impact of present and future aircraft NOxand aerosol emissions on atmospheric composition and associated direct radiative forcing of climate

Abstract. Aviation NOx emissions not only have an impact on global climate by changing ozone and methane levels but also contribute to the deterioration of local air quality. A new version of the LMDZ-INCA global model, including chemistry of both the troposphere and the stratosphere and the sulfate-nitrate-ammonium cycle, is applied to re-evaluate the impact of aircraft NOx and aerosol emissions on climate. The results confirm that the efficiency of NOx to produce ozone is very much dependent on the injection height; it increases with the background methane and NOx concentrations and with decreasing aircraft NOx emissions. The methane lifetime variation is less sensitive to the location of aircraft NOx emissions than the ozone change. The net NOx radiative forcing (RF) (O3+CH4) is largely affected by the revised CH4 RF formula. The ozone positive forcing and the methane negative forcing largely offset each other, resulting in a slightly positive forcing for the present day. However, in the future, the net forcing turns to negative, essentially due to higher methane background concentrations. Additional RFs involving particle formation arise from aircraft NOx emissions since the increased hydroxyl radical (OH) concentrations are responsible for an enhanced conversion of SO2 to sulfate particles. Aircraft NOx emissions also increase the formation of nitrate particles in the lower troposphere. However, in the upper troposphere, increased sulfate concentrations favour the titration of ammonia leading to lower ammonium nitrate concentrations. The climate forcing of aircraft NOx emissions is likely to be small or even switch to negative (cooling), depending on atmospheric NOx or CH4 future background concentrations, or when the NOx impact on sulfate and nitrate particles is considered. However, large uncertainties remain for the NOx net impact on climate and in particular on the indirect forcings associated with aerosols, which are even more uncertain than the other forcings from gaseous species. Hence, additional studies with a range of models are needed to provide a more consolidated view. Nevertheless, our results suggest that reducing aircraft NOx emissions is primarily beneficial for improving air quality.

EPR spectroscopic evidence of iron-catalysed free radical formation in chronic mountain sickness: Dietary causes and vascular consequences

Chronic mountain sickness (CMS) is a high-altitude (HA) maladaptation syndrome characterised by elevated systemic oxidative-nitrosative stress (OXNOS) due to a free radical-mediated reduction in vascular nitric oxide (NO) bioavailability. To better define underlying mechanisms and vascular consequences, this study compared healthy male lowlanders (80 m, n = 10) against age/sex-matched highlanders born and bred in La Paz, Bolivia (3600 m) with (CMS+, n = 10) and without (CMS-, n = 10) CMS. Cephalic venous blood was assayed using electron paramagnetic resonance spectroscopy and reductive ozone-based chemiluminescence. Nutritional intake was assessed via dietary recall. Systemic vascular function and structure were assessed via flow-mediated dilatation, aortic pulse wave velocity and carotid intima-media thickness using duplex ultrasound and applanation tonometry. Basal systemic OXNOS was permanently elevated in highlanders (P = <0.001 vs. lowlanders) and further exaggerated in CMS+, reflected by increased hydroxyl radical spin adduct formation (P = <0.001 vs. CMS-) subsequent to liberation of free ‘catalytic’ iron consistent with a Fenton and/or nucleophilic addition mechanism(s). This was accompanied by elevated global protein carbonylation (P = 0.046 vs. CMS-) and corresponding reduction in plasma nitrite (P = <0.001 vs. lowlanders). Dietary intake of vitamins C and E, carotene, magnesium and retinol were lower in highlanders and especially deficient in CMS + due to reduced consumption of fruit and vegetables (P = <0.001 to 0.028 vs. lowlanders/CMS-). Systemic vascular function and structure were also impaired in highlanders (P = <0.001 to 0.040 vs. lowlanders) with more marked dysfunction observed in CMS+ (P = 0.035 to 0.043 vs. CMS-) in direct proportion to systemic OXNOS (r = −0.692 to 0.595, P = <0.001 to 0.045). Collectively, these findings suggest that lifelong exposure to iron-catalysed systemic OXNOS, compounded by a dietary deficiency of antioxidant micronutrients, likely contributes to the systemic vascular complications and increased morbidity/mortality in CMS+. Trial registryClinicalTrials.gov; No: NCT01182792; URL: www.clinicaltrials.gov.

Influencing surface phenomena by Au diffusion in buffered TiO2-Au thin films: Effects of deposition and annealing processing

Enhanced optical properties of TiO2 thin films can be achieved by doping or coating with metals. Metal-doped TiO2 can reduce electron-hole recombination and increase hydroxyl radical concentration on the surface of TiO2, resulting in increase of the photocatalytic activity. TiO2 and TiO2-Au thin films were obtained by DC magnetron sputtering of Ti target with Ar ions in O2 atmosphere. In the case of Au buffered TiO2 thin films, two different systems were deposited for comparison. Post deposition annealing at 400 °C was carried out in nitrogen atmosphere for 3 h. The structural and optical characteristics of the prepared films were investigated in detail by the combination of high-resolution microscopic and spectroscopic techniques. The photo-degradation rate was measured using Rhodamine B which simulated pollutant. Post deposition annealing resulted in diffusion of Au atoms through the layer as it was revealed by transmission electron microscopy and energy dispersive X-ray spectroscopy. The obtained TiO2 thin films were found to be amorphous after deposition and annealing at 400 °C leads to crystallization of anatase phase. Analysis of the binding energy in the corresponding X-ray photoelectron spectra has confirmed stoichiometry of TiO2 and that concentration of Au on the surface can be controlled by sputtering and annealing conditions, thus changing optical properties by influencing the surface plasmonic nature. All Au doped TiO2 thin films exhibited enhanced wettability and photo-degradation rates when compared to pristine titania films.

MYCN upregulates the transsulfuration pathway to suppress the ferroptotic vulnerability in MYCN-amplified neuroblastoma.

Ferroptosis is an iron-dependent, oxidative form of cell death that is countered mainly by glutathione peroxidase 4 (GPX4) and the production of glutathione (GSH), which is formed from cysteine. The identification of the cancers that may benefit from pharmacological ferroptotic induction is just emerging. We recently demonstrated that inducing ferroptosis genetically or pharmacologically in MYCN-amplified neuroblastoma (NB) is a novel and effective way to kill these cells. MYCN increases iron metabolism and subsequent hydroxyl radicals through increased expression of the transferrin receptor 1 (TfR1) and low levels of the ferroportin receptor. To counter increased hydroxyl radicals, MYCN binds to the promoter of SLC3A2 (solute carrier family 3 member 2). SLC3A2 is a subunit of system Xc-, which is the cysteine-glutamate antiporter that exports glutamate and imports cystine. Cystine is converted to cysteine intracellularly. Here, we investigated other ways MYCN may increase cysteine levels. By performing metabolomics in a syngeneic NB cell line either expressing MYCN or GFP, we demonstrate that the transsulfuration pathway is activated by MYCN. Furthermore, we demonstrate that MYCN-amplified NB cell lines and tumors have higher levels of cystathionine beta-synthase (CBS), the rate-limiting enzyme in transsulfuration, which leads to higher levels of the thioether cystathionine (R-S-(2-amino-2-carboxyethyl)-l-homocysteine). In addition, MYCN-amplified NB tumors have high levels of methylthioadenosine phosphorylase (MTAP), an enzyme that helps salvage methionine following polyamine metabolism. MYCN directly binds to the promoter of MTAP. We propose that MYCN orchestrates both enhanced cystine uptake and enhanced activity of the transsulfuration pathway to counteract increased reactive oxygen species (ROS) from iron-induced Fenton reactions, ultimately contributing to a ferroptosis vulnerability in MYCN-amplified neuroblastoma.

Persistent free radicals in biochar enhance superoxide-mediated Fe(III)/Fe(II) cycling and the efficacy of CaO2 Fenton-like treatment

Superoxide radicals (O2•-) produced by the reaction of Fe(III) with H2O2 can regenerate Fe(II) in Fenton-like reactions, and conditions that facilitate this function enhance Fenton treatment. Here, we developed an efficient Fenton-like system by using calcium peroxide/biochar (CaO2/BC) composites as oxidants and tartaric acid-chelated Fe(III) as catalysts, and tested it for enhanced O2•--based Fe(II) regeneration and faster sulfamethoxazole (SMX) degradation. SMX degradation rates and peroxide utilization efficiencies were significantly higher with CaO2/BC than those with CaO2 or H2O2 lacking BC. The CaO2/BC system showed superior activity to reduce Fe(III), while kinetic analyses using chloroform as a O2•- probe inferred that the O2•- generation rate by CaO2/BC was one-half of that by CaO2. Apparently, O2•- is utilized more efficiently in this system to regenerate Fe(II) and enhance SMX degradation. Additionally, a positive correlation between SMX degradation rate constants and EPR signal intensities of biochar-derived persistent free radicals (PFRs) in CaO2/BC was obtained. We postulate that PFRs enhanced Fe(III) reduction by shuttling electrons donated by O2•-. This represents a new strategy to augment the ability of superoxide to accelerate Fe(III)/Fe(II) cycling for increased hydroxyl radical production and organic pollutant removal in Fenton-like reactions.

Impact of UV-LED photoreactor design on the degradation of contaminants of emerging concern

Recent developments in UV-LED technology open up new possibilities for water treatment. TiO2 photocatalysis can benefit from optimized photoreactor design to increase hydroxyl radical production and reduce its electrical energy per order (EEO) demands, which still ranks high among advanced oxidation processes. However, literature on UV-LED photoreactor design is largely lacking. In this work, a detailed investigation of photoreactor design is proposed. The simulation of a lab scale cylindrical reactor with 8 different UV-LED arrays was run with the professional version of an optic software. The increase of radiant flux and irradiance on the reactor’s middle cross section and side walls, respectively, was related to an increasing number of LEDs and to a shorter distance from the reactor but not necessarily to an increase in homogeneity of light distribution. A full factorial experimental design was applied to evaluate the degradation of a representative contaminant of emerging concern (ciprofloxacin) considering 4 independent variables and their interactive effects on kinetic rates and EEO values. The significance of these effects was evaluated with ANOVA and a prediction model was established. The results show that the presence of a TiO2 nanofilm was the most significant tested effect. The number of LEDs, their distance from the reactor’s wall and the adoption of controlled periodic illumination also greatly influenced kinetic rates but were less relevant for reducing EEO values because the energetic trade-off was not sufficient to turn the kinetic gain into lower electricity demands.

Secondary aerosol formation from a Chinese gasoline vehicle: Impacts of fuel (E10, gasoline) and driving conditions (idling, cruising)

Chassis dynamometer experiments were conducted to investigate the effect of vehicle speed and usage of ethanol-blended gasoline (E10) on formation and evolution of gasoline vehicular secondary organic aerosol (SOA) using a Gothenburg Potential Aerosol Mass (Go: PAM) reactor. The SOA forms rapidly, and its concentration exceeds that of primary organic aerosol (POA) at an equivalent photochemical age (EPA) of ~1 day. The particle effective densities grow from 0.62 ± 0.02 g cm−3 to 1.43 ± 0.07 g cm−3 with increased hydroxyl radical (OH) exposure. The maximum SOA production under idling conditions (4259–7394 mg kg-fuel−1) is ~20 times greater than under cruising conditions. There was no statistical difference between SOA formation from pure gasoline and its formation from E10. The slopes in Van Krevelen diagram indicate that the formation pathways of bulk SOA includes the addition of both alcohol/peroxide functional groups and carboxylic acid formation from fragmentation. A closure estimation of SOA based on bottom-up and top-down methods shows that only 16%–38% of the measured SOA can be explained by the oxidation of measured volatile organic compounds (VOCs), suggesting the existence of missing precursors, e.g. unmeasured VOCs and probably semivolatile or intermediate volatile organic compounds (S/IVOCs). Our results suggest that applying parameters obtained from unified driving cycles to model SOA concentrations may lead to large discrepancies between modeled and ambient vehicular SOA. No reduction in vehicular `SOA production is realized by replacing normal gasoline with E10.