OH Radicals Research Articles

Cascade Hydroxyl Radical-Generating and Ferroptosis-Inducing Nanofiber System for the Therapy of Oral Squamous Cell Carcinoma.

Nanofiber (NF) membrane systems that can provide cascade catalytic reaction and ferroptosis induction were developed for oral cancer therapy. Glucose oxidase (GOx) and aminoferrocene (AF) were introduced into the NF system for glucose deprivation/H2O2 generation and OH radical generation, respectively. GOx offers starvation therapy and AF (including iron) provides chemodynamic therapy/ferroptosis for combating oral cancer. GOx (water-soluble) and AF (poorly water-soluble) molecules were successfully entrapped in the NF membrane via an electrospinning process. GOx and AF were incorporated into the polyvinyl alcohol (PVA)-based NF, resulting in PVA/GOx/AF NF with fast disintegration and immediate drug-release properties. In oral squamous cell carcinoma (YD-9 cells), the PVA/GOx/AF NF group exhibited higher cytotoxicity, antiproliferation potential, cellular ROS level, apoptosis induction, lipid ROS level, and malondialdehyde level compared to the other NF groups. The electrospun PVA/GOx/AF NF can be directly applied to oral cancer without causing pain, offering starvation/chemodynamic therapy and ferroptosis induction.

Oxidation of Aminoacetaldehyde Initiated by the OH Radical: A Theoretical Mechanistic and Kinetic Study

Oxidation of Aminoacetaldehyde Initiated by the OH Radical: A Theoretical Mechanistic and Kinetic Study

Soft X-ray Induced Radiation Damage in Dip-and-Pull Photon Absorption and Photoelectron Emission Experiments.

X-ray irradiation can induce chemical reactions on surfaces. In X-ray spectroscopic experiments, such reactions may result in spectrum distortion and are termed radiation damage. In this study, we investigate the X-ray-induced chemical reaction at the partially oxidized copper surface in the settings of the dip-and-pull experiment, a method that generates liquid-solid interfaces for in situ X-ray photoelectron spectroscopy (XPS) studies. In dense water vapor resembling the predipping condition, a series of time-elapsed X-ray absorption spectra acquired in total electron yield mode (TEY-XAS) shows that X-ray exposure causes copper reduction, which follows first-order kinetics and occurs only at the surface shallower than the probing depth of TEY-XAS. At the solid-water interface created by the dip-and-pull method, the chemical reduction of surface copper is also identified by XPS. We conclude that the reduction is driven by the product of water radiolysis, where the reducing solvated electron prevails against the oxidizing OH radical and results in an overall reduction of surface copper ions.

Phytochemical characterization, biochemical profiling and evaluation of anticancer potential of methanolic extract of Withania somnifera stem.

Phytotherapy employs phytoconstituents/phytomedicines derived from plants for treating and preventing illnesses. Withania somnifera is known in the Indian Ayurveda Pharmacopoeia for its medicinal applications and pharmacological properties. In this study, we examined the biological activity spectrum of Withania somnifera methanolic extract of stem (WSME), which is valued as a "Rasayana" due to its extensive range of medicinal uses. WSME was subjected to TPC and TFC quantification and bioactive components were characterized using LC-MS. Its antioxidant potential was gauged by DPPH and H2O2 radical scavenging assays, while antibacterial efficacy was assessed against S.aureus and E.coli using disc diffusion assay. In vitro anticancer activity was evaluated against human breast cancer MDA-MB-231 cells while toxicity was evaluated against normal Vero cells using MTT assay. WSME, rich in Withaferin A, showed TPC of 4.73±0.15 mg GAE/g and TFC of 94.94±6.15 mg QE/g dry weight of extract. It exhibited significant antioxidant activity (43.28 and 66.8 % inhibition at 1,000 μg/mL using DPPH and H2O2 assays, respectively) and mild antibacterial effects against S.aureus (300-500 mg/mL). WSME induced cell death in MDA-MB-231 cells and significantly inhibited their growth (IC50: 66 μg/mL, P value<0.05) without affecting normal Vero cells in the studied range of 25-400 μg/mL (IC50: 6.09 mg/mL, P value>0.05). The present study lends support to further testing of WSME against other cancer cell lines and animal models of cancer. These preclinical studies would provide further validation to its prospective use as an adjunct in human breast cancer therapy.

Insights for Precursors Influence on the Solar-Assisted Photocatalysis of Greenly Synthesizing Zinc Oxide NPs towards Fast and Durable Wastewater Detoxification

Herein, this study has examined the influence of Zn2+ sources during a biogenic-mediated pathway to synthesize ZnO nanoparticles with highly desirable solar-responsive catalytic properties. Salts of nitrate, acetate and chloride have been utilized. The ZnO powders underwent characterization using diverse analytical tools, including XRD, FTIR, Raman, BET, SEM, TEM with EDS/elemental mapping and UV-vis absorption/emission spectroscopic analyses. Accordingly, precursors have proved to affect crystallinity, morphology, surface characteristics, optical properties and the photocatalytic degradation of methylene blue (MB) model pollutant. It was observed that ZnO derived from zinc acetate precursor (Z-AC NPs) exhibits very fast photocatalytic degradation of MB at pH 11 with superior kinetic estimates of 0.314 min−1 and t1/2 = 2.2 min over many of recent reports. In contrast, the chloride precursor is not recommended along with the employed biogenic route. The intriguing findings could be directly correlated to the decreased crystal size, augmented surface area, the hexagonal morphology of the crystals, high potency in absorbing visible photons, high efficacy in separating photogenerated charge carriers and producing high amounts of •OH radicals. Further testing of Z-AC NPs in photocatalytic remediation of water samples from Dumat Aljandal Lake in Aljouf, Saudi Arabia, contaminated with MB and pyronine Y (PY) dyestuffs, showed high dye photodegradation. Therefore, this work could lead to an extremely fast avenue for decontaminating wastewater from hazmat dyestuff.

Clarifying the Direct Generation of •OH Radicals in Photocatalytic O2 Reduction: Theoretical Prediction Combined with Experimental Validation.

This work systematically studied thermocatalytic and photocatalytic pathways of formaldehyde degradation and H-assisted O2 reduction over a Pt13/anatase-TiO2(101) composite via DFT calculations together with constrained molecular dynamics (MD) simulations. We show that photocatalytic O2 reduction on Pt/TiO2 can directly generate •OH radicals (*O2 → *OOH → •OH) via two hydrogenation steps with small barriers, and the product selectivity (*H2O2 or •OH) is decided by the relative position between catalyst Fermi level and •OH/*H2O2 redox potential (theoretical determination of 0.07 V referencing to the SHE). Such a novel reaction channel was furthermore validated at the liquid-solid interface via constrained MD simulations and experimental electron paramagnetic resonance detections, and a wide range of H resources, e.g., *HCHO, *HCO, *H (H+ + e-), can always drive the direct •OH generation. The additional portion of e--triggered •OH radicals are prone to diffuse into solution or the TiO2 surface and furthermore cooperate with the conventional h+-driven photooxidations.

Wintertime ozone surges: The critical role of alkene ozonolysis

Ozone (O3) pollution is usually linked to warm weather and strong solar radiation, making it uncommon in cold winters. However, an unusual occurrence of four high O3 episode days (with maximum hourly concentrations exceeding 100 ppbv and peaking at 121 ppbv) was recorded in January 2018 in Lanzhou city, China. During these episodes, the average daytime concentration of total non-methane volatile organic compounds (TVOCs) reached 153.4 ± 19.0 ppbv, with alkenes—largely emitted from the local petrochemical industry—comprising 82.3 ± 13.1 ppbv. Here we show a photochemical box model coupled with a Master Chemical Mechanism to elucidate the mechanisms behind this unusual wintertime O3 pollution. We find that the typically low temperatures (−1.7 ± 1.3 °C) and weak solar radiation (263.6 ± 60.7 W m-2) of those winter episode days had a minimal effect on the reactivity of VOCs with OH radicals. Instead, the ozonolysis of alkenes generated Criegee intermediates, which rapidly decomposed into substantial ROx radicals (OH, HO2, and RO2) without sunlight. This radical production led to the oxidation of VOCs, with alkene ozonolysis ultimately contributing to 89.6 ± 8.7% of the O3 formation during these episodes. This mechanism did not activate at night due to the depletion of O3 by the NO titration effect. Furthermore, the findings indicate that a reduction of alkenes by 28.6% or NOx by 27.7% in the early afternoon could significantly mitigate wintertime O3 pollution. Overall, this study unravels the unique mechanism of alkene-induced winter O3 pollution and offers a reference for winter O3 reduction strategies in the petrochemical industrial regions.

Measurements of Atmospheric HO2 Radicals Using Br-CIMS with Elimination of Potential Interferences from Ambient Peroxynitric Acid.

As a promising direct measurement method of atmospheric hydroperoxyl radicals (HO2), bromide chemical ionization mass spectrometry (Br-CIMS) has been first demonstrated by Sanchez et al. (Atmos. Meas. Tech. 2016, 9, 3851-3861). However, field application of this method is currently still sparse, and there is still a gap between measured HO2 concentrations and calculated ones derived from the atmospheric equilibrium between HO2 and peroxynitric acid (HO2NO2). In this work, we constructed an improved Br-CIMS with optimizations of custom-built front-end devices, chamber pressures, and instrumental voltages to achieve a 3σ detection limit of 0.5 ppt at an integration time of 60 s and a sensitivity of 1-3 cps ppt-1 under a total reagent ion signal of 0.2 MHz for HO2 detection. HO2NO2, a product from atmospheric reactions between HO2 and NO2, can also be detected by Br-CIMS, whose interference on the HO2 measurement was found but nearly eliminated by regulating key CIMS voltages to minimize the decomposition of (BrHO2NO2)- ions in the MS. In addition, a 2 week field campaign was carried out in urban Shanghai, demonstrating that the interference of HO2 from ambient HO2NO2 was less than 10% of the true HO2 signal under our optimized CIMS voltage setting. Our study suggests that Br-CIMS is a reliable technique for atmospheric HO2 measurements.

Novel S-scheme β-Cu2V2O7/Ni/Pg-C3N4 heterojunction photocatalyst for sunlight-induced degradation of RhB

A novel S-scheme β-Cu2V2O7/Ni/Pg-C3N4 nanocomposite photocatalyst has been advantageously established by propelling β-Cu2V2O7 nanoparticles (NPs) on the top layer of porous graphitic carbon nitride (Pg-C3N4) nanosheets (NSs) using a facile co-precipitation approach. Implementing photoelectrochemical and physicochemical techniques, the crystallinity, purity, optical quality, morphology, chemical composition, and charge separation efficiency of the produced samples were examined. The outcomes indicate that metallic Ni and β-Cu2V2O7 NPs were perfectly encapsulated onto the Pg-C3N4 NSs and well-matched band structures between both semiconductors facilitate the creation of an S-scheme charge transfer path. The fabricated pristine and β-Cu2V2O7/Ni/Pg-C3N4 composite samples were utilized as a catalyst for the removal of rhodamine B (RhB) dye under sunlight irradiation. The β-Cu2V2O7/Ni/Pg-C3N4 nanocomposite exhibits exceptional activity within 60 min of radiation exposure (RhB- 98.56%), whereas β-Cu2V2O7 and Pg-C3N4 show reduced activity (RhB-34.4% and 45.68%). The favourable impact of S-scheme nanocomposite establishment boosted photocatalytic behavior using the intrinsic electric field among Pg-C3N4 NSs and β-Cu2V2O7 and surface plasmon resonance (SPR) effect of metallic Nickel (Ni) NPs for delivering e− and h+ pairs and prolonging the life of charge carriers. According to radical scavenging experiments •O2− is the primary reactive species followed by •OH radicals. The produced nanocomposite has the potential to be employed in large-scale photocatalytic water treatment, as evidenced by the photocatalyst's excellent efficiency and reusability after five consecutive experiments.

Artificial Photosynthesis: Visible Light-Activated TiOCl&lt;sub&gt;2&lt;/sub&gt;/2-Phenyl Indole Complexes for Atmospheric CO&lt;sub&gt;2&lt;/sub&gt; and H&lt;sub&gt;2&lt;/sub&gt;O Capture and Long-Chain Organic Products Generation

We present a novel self-organized chemical "living" system that mimics natural photosynthesis by capturing CO2 and H2O from the atmosphere at ambient conditions. This system autonomously reduces CO2 with H2O protons to produce long-chain aliphatic oxygenated products. Starting with 2-phenyl indole (PI) complexes with TiCl4, the hydrolyzed complexes react with CO2 to form organotitanium carbonates. The 2:1 PI/TiCl4 complex was found to be the most effective. Key findings include: Photocatalytic Reduction: Visible light reduces TiIV to TiIII and TiII, forming peroxotitanium complexes and releasing OH radicals. CO2 Reduction: CO2 is reduced to CO, H2CO, and CH3OH, which couple to form HOCH2CH2OH. Organic Compound Synthesis: The system generates oxygenated organic compounds with carbon chains from C2 to C16. Ligand Exchange: The PI ligand exchanges with donor molecules, forming adducts involved in the photocatalytic process. PI Oligomerization: Contributes to the formation of PI oligomers. These processes were monitored using matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) spectra, proton and Carbon-13 nuclear magnetic resonance (13C NMR), and infrared (IR) spectra, identifying over two dozen intermediates and products. This system offers a prototype for new applications with potential improvements using other metals and ligands.

Improving HONO Simulations and Evaluating Its Impacts on Secondary Pollution in the Yangtze River Delta Region, China

AbstractSecondary air pollution, especially ozone (O3) and secondary aerosols, are emerging air quality challenges confronting China. Nitrous acid (HONO), as the predominant source of hydroxyl radicals (OH), are acknowledged to be essential for secondary pollution. However, HONO concentrations are usually underestimated by current air quality models due to the inadequate representations of its sources. In the present study, we revised the Weather Research and Forecasting &amp; Chemistry (WRF‐Chem) model by incorporating additional HONO sources, including primary emissions, photo‐/dark oxidation of NOx, heterogeneous uptake of NO2 on surfaces, and nitrate photolysis. By combining in‐situ measurements in the Yangtze River Delta (YRD) region, we found the improved model show much better performance on HONO simulation and is capable of reproducing observed high concentrations. The source‐oriented method is employed to quantitatively understand the relative importance of various processes, which showed that heterogeneous NO2 uptake on the ground surface was the major contributor to HONO formation in urban areas. Comparatively, photo‐oxidation of NOx is a main contributor in rural areas. The introduction of multiple sources of HONO led to an apparent increase in OH and hydroperoxyl (HO2) radicals. The promoted HO2 levels further increased diurnal O3 concentration by 4.5–12.9 ppb, while secondary inorganic and organic concentrations were also increased by 14%–32% during a typical secondary pollution event. The improved description of HONO emission and formation in the model substantially narrowed the gaps between simulations and observations, highlighting the great importance in understanding and numerical representations of HONO in secondary pollution study.

Effect of dissolved oxygen on the peroxymonosulfate activation pathway in an electrochemical Co/P/CA cathode system

Although dissolved oxygen plays an important role in electro-Fenton-like processes, few investigations have revealed its underlying effects in such processes. Herein, the effect of dissolved oxygen on peroxide activation in an electro-Fenton-like system comprising electrochemical cells and peroxymonosulfate (PMS) was investigated. Cobalt phosphide-modified carbon aerogel (Co/P/CA) was used as the cathode material owing to the high conductivity and catalytic activity of Co/P/CA. Several free radicals and their effects on organic pollutant removal were observed using electron paramagnetic resonance spectrometry and quenching experiments, respectively. The observations revealed that in the presence of O2, hydroxyl radical (·OH), superoxide (O2−·), and singlet oxygen (1O2) served as the primary active species in the PMS activation process, while in the presence of N2, ·OH and sulfate radical (SO4−·) served as the dominant active species in this process. The factor responsible for the difference in the PMS activation pathways available under O2 and N2 conditions was investigated using rotating disk electrode tests and free energy calculations. The tests indicated that O2 facilitates PMS activation to form ·OH instead of SO4−·. The dissolved oxygen subsequently underwent a single-electron-reduction reaction and was converted into O2−·, which could serve as a source of 1O2. When N2 was introduced, Co species, particularly Co(II), played a key role in activating PMS. The free radicals ·OH and SO4−· were generated during the PMS activation process. This study clearly demonstrates the mediating catalysis role of dissolved oxygen in electro-Fenton-like system through experimental data and theoretical calculations, thereby positively contributing to future studies regarding the continuous activation of peroxides in composite systems and improvement of the efficiency of waterbody remediation.

Development of Next Generation Membranes for PEM Water Electrolysis in AGC

AGC’s FORBLUETM product family has over 70 years of experience in ion-exchange membranes (IEMs). S-SERIES, a FORBLUETM member, is a per-fluorinated sulfonic acid polymer (PFSA) membrane utilized in various electrochemical devices and industrial electrolysis. AGC’s IEM technology had a lot of experience in the chlor-alkali application and was further developed for the PEM water electrolysis industry.AGC R&D has developed S-SERIES membranes with a smaller thickness, improved reinforcement, and high ion exchange capacity (IEC) that enhanced not only an electrochemical performance but also dimensional stability.A membrane electrode assembly (MEA) was fabricated using a developed membrane with high IEC polymer (IEC 1.25 meq/g). As a result, IV characterization of a single cell with 25 cm2 electrode area at 80°C showed a significant voltage reduction compared to a commercial membrane in the PEM water electrolysis market. In addition, H2 crossover during the electrolysis was evaluated in a single cell with a 25 cm2 electrode area at 80°C and ambient pressure, and the H2 concentration in O2 at the anode side was compared at a current density of 1.0 A/cm2. The developed membrane showed 0.3 vol% H2 crossover, whereas the commercial membrane showed 0.5 vol%.Furthermore, next-generation membranes with gas recombination catalysts (GRC) and radical scavengers leading to lower gas crossover and higher chemical stability are under development. Recently, high-pressure electrolyzers have been getting more attention and the increase of H2 crossover is a concern against the lower explosive limit (LEL) for hydrogen in oxygen. In general, PFSA membranes are considered to have high chemical durability, however, F ion release is observed, that indicate that this PFSA polymer is attacked by OH radicals generated in the PEM water electrolysis system. AGC has been investigating the application of GRC and radical scavengers to the newly developed membranes. It was evaluated in a single cell with 25 cm2 electrode area at 80°C and 2.0 A/cm2. As a result, the H2 crossover and F ions release rate (FRR) were reduced compared to the membrane without both additives. The data will be presented on these improved performances.

(Dielectric Science and Technology Division Poster Award, 3rd Place) Radical Oxidation for Enhancing Polishing-Rate and Improving Slurry Stability in Ag-Film Chemical–Mechanical-Planarization

Recently, Ag-film has been utilized as a reflective layer in organic-light-emitting- diode on silicion(OLEDoS). The formation of a reflective Ag-film layer was conducted by Ag-film deposition and following Ag-film chemical-mechanical planarization (CMP). The Ag-film has ductility property (i.e., hardness of 0.3 GPa) so that a reletively soft CMP pad should be used to minimize the generation of the CMP induced scratches. However, using a soft CMP pad, it is notably difficult to achieve a high Ag-film polishing-rate (i.e., 300 nm/min). Thus, to enhance Ag-film polishing-rate, a Fenton reaction between ferric ions and H2O2 has been applied. Although, a Fenton reaction enhancing dissolved oxygen concentration can increase remarkably the Ag-film polishing-rate, the CMP slurry using Fenton reaction has produced a detrimental slurry stability after mixing with H2O2 (i.e., extremely low H2O2 pot life time. In this study, as a solution, the Ag-film CMP slurry was designed via radical oxidation on the Ag-film surface during CMP, without using Fenton reaction (i.e., mixing ferric ions with H2O2). The radical oxidation was achived by using halide oxidant (i.e., H5IO6), which radical oxidation degree principally depended on halide oxidant concentration and slurry pH, showing a notable high Ag-film polishing-rate (i.e., 400 nm/min) without the precence of corrosion. Without using Fenton reaction, the secondary diameter of colloidal abrasives in the designed Ag-film CMP slurry was not changed for several months. In our presentation, we will prove the mechanism of the radical oxidation on the polished Ag-film surface. In addition, we will present the dependencies of the chemical dominant polishing properties (i.e., OH radical, chemical oxidation degree of the Ag-film surfcae, chemical composition of chemical oxidation, slurry adsortion degree, and corrosion potential and current) as well as the mechanical dominant polishing properties (i.e., electrostatic force between abrasives and Ag-film surface) on the halid oxidant concentration.

Hypoxia Reversion and STING Pathway Activation through Large Mesoporous Nanozyme for Near-Infrared-II Light Amplified Tumor Polymetallic-Immunotherapy.

cGAS/STING pathway, which is highly related to tumor hypoxia, is considered as a potential target for remodeling the immunosuppressive microenvironment of solid tumors. Metal ions, such as Mn2+, activate the cGAS/STING pathway, but their efficacy in cancer therapy is limited by insufficient effect on immunogenic tumor cell death of a single ion. Here, we evaluate the association between tumor hypoxia and cGAS/STING inhibition and report a polymetallic-immunotherapy strategy based on large mesoporous trimetal-based nanozyme (AuPdRh) coordinated with Mn2+ (Mn2+@AuPdRh) to activate cGAS/STING signaling for robust adaptive antitumor immunity. Specifically, the inherent CAT-like activity of this polymetallic Mn2+@AuPdRh nanozyme decomposes the endogenous H2O2 into O2 to relieve tumor hypoxia induced suppression of cGAS/STING signaling. Moreover, the Mn2+@AuPdRh nanozyme displays a potent near-infrared-II photothermal effect and strong POD-mimic activity; and the generated hyperthermia and •OH radicals synergistically trigger immunogenic cell death in tumors, releasing abundant dsDNA, while the delivered Mn2+ augments the sensitivity of cGAS to dsDNA and activates the cGAS-STING pathway, thereby triggering downstream immunostimulatory signals to kill primary and distant metastatic tumors. Our study demonstrates the potential of metal-based nanozyme for STING-mediated tumor polymetallic-immunotherapy and may inspire the development of more effective strategies for cancer immunotherapy.

A Novel Cerium Oxide/Gold/Carbon Nanocomposite-Based Electrochemical Sensor for Detecting Hydroxyl Radicals

Hydroxyl radicals (•OH), a type of reactive oxygen species (ROS), play a crucial role in maintaining the normal physiological processes of human cells. Nevertheless, an excessive accumulation of these radicals may perturb cellular mechanisms, so triggering the onset of severe diseases, including cancer, neurological disorders, and heart disease. The detection of •OH is thus of utmost importance in the early diagnosis of these disorders. The combination of an electrochemical methodology with a recognition system is considered as a promising approach for the detection of •OH. This is primarily due to its capacity to provide fast and direct readings without the need for any preliminary sample preparation. This study presents the development of a new electrochemical sensor for the detection of •OH. The sensor was developed by modifying a screen-printed carbon electrode (SPCE) with a nanocomposite consisting of cerium oxide nanoclusters (CeOx), gold nanoparticles (AuNPs), and a highly conductive carbon. The synthesis of AuNPs supported by carbon was carried out using a deposition-precipitation process. Subsequently, the meticulous deposition of CeOx nanoclusters onto the AuNPs was achieved by the use of surface organometallic chemistry (SOMC). Energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM) were applied to assess the distribution of AuNPs on the carbon substrate and their subsequent embellishment with CeOx nanoclusters. The actual loadings of Ce and Au present in the nanocomposite were measured using inductively coupled plasma optical emission spectroscopy (ICP-OES). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to analyze the electrochemical responses resulting from the interaction of the CeOx-Au/Carbon nanocomposite with •OH. The CV results demonstrated that the proposed sensor exhibited the capability to effectively identify the presence of •OH in the Fenton reaction, with a notably low limit of detection of 58 µM. The sensor demonstrated a linear correlation between the current response and the concentration of •OH, within the range of 0.05 to 5 mM. Compared to a sensor modified with CeOx/Carbon, the CeOx-Au/Carbon-modified sensor exhibited enhanced electrochemical performance, as demonstrated by an increased current response and a reduced peak potential difference when detecting •OH radicals. Furthermore, the EIS studies showed that the sensor could distinguish •OH from other comparable ROS, such as hydrogen peroxide (H2O2).

Coupling Electro-Fenton and Electrocoagulation of Aluminum-Air Batteries for Enhanced Tetracycline Degradation: Improving Hydrogen Peroxide and Power Generation.

Electro-Fenton (EF) technology has shown great potential in environmental remediation. However, developing efficient heterogeneous EF catalysts and understanding the relevant reaction mechanisms for pollutant degradation remain challenging. We propose a new system that combines aluminum-air battery electrocoagulation (EC) with EF. The system utilizes dual electron reduction of O2 to generate H2O2 in situ on the air cathodes of aluminum-air batteries and the formation of primary cells to produce electricity. Tetracycline (TC) is degraded by ·OH produced by the Fenton reaction. Under optimal conditions, the system exhibits excellent TC degradation efficiency and higher H2O2 production. The TC removal rate by the reaction system using a graphite cathode reached nearly 100% within 4 h, whereas the H2O2 yield reached 127.07 mg/L within 24 h. The experimental results show that the novel EF and EC composite system of aluminum-air batteries, through the electroflocculation mechanism and ·OH and EF reactions, with EC as the main factor, generates multiple •OH radicals that interact to efficiently remove TC. This work provides novel and important insights into EF technology, as well as new strategies for TC removal.

Kalanchoe tomentosa: Phytochemical Profiling, and Evaluation of Its Biological Activities In Vitro, In Vivo, and In Silico.

In this work, the leaves of K. tomentosa were macerated with hexane, chloroform, and methanol, respectively. The phytochemical profiles of hexane and chloroform extracts were unveiled using GC/MS, whereas the chemical composition of the methanol extract was analyzed using UPLC/MS/MS. The antibacterial activity of extracts was determined against gram-positive and gram-negative strains through the minimal inhibitory concentration assay, and in silico studies were implemented to analyze the interaction of phytoconstituents with bacterial peptides. The antioxidant property of extracts was assessed by evaluating their capacity to scavenge DPPH, ABTS, and H2O2 radicals. The toxicity of the extracts was recorded against Artemia salina nauplii and Caenorhabditis elegans nematodes. Results demonstrate that the hexane and chloroform extracts contain phytosterols, triterpenes, and fatty acids, whereas the methanol extract possesses glycosidic derivatives of quercetin and kaempferol together with sesquiterpene lactones. The antibacterial performance of extracts against the cultured strains was appraised as weak due to their MIC90 values (>500 μg/mL). As antioxidants, treatment with extracts executed high and moderate antioxidant activities within the range of 50-300 μg/mL. Extracts did not decrease the viability of A. salina, but they exerted a high toxic effect against C. elegans during exposure to treatment. Through in silico modeling, it was recorded that the flavonoids contained in the methanol extract can hamper the interaction of the NAM/NAG peptide, which is of great interest since it determines the formation of the peptide wall of gram-positive bacteria. This study reports for the first time the biological activities and phytochemical content of extracts from K. tomentosa and proposes a possible antibacterial mechanism of glycosidic derivatives of flavonoids against gram-positive bacteria.

Intravascular Casting Radiopaque Hydrogel Systems for Transarterial Chemo/Cascade Catalytic/Embolization Therapy of Hepatocellular Carcinoma.

This paper introduces catheter-directed intravascular casting hydrogels for transarterial chemo/starvation/chemodynamic embolization (TACSCE) therapy of hepatocellular carcinoma (HCC). Comprising Mn ion-crosslinked hyaluronic acid-dopamine (HD) with glucose oxidase (for glucose decomposition to H2O2 in starvation therapy), doxorubicin (for chemotherapy), and iopamidol (for X-ray imaging), these hydrogels are fabricated for transarterial embolization therapy guided by X-ray fluoroscopy. Mn4+ (from MnO2) demonstrates strong coordination with the catechol group of HD, providing hypoxia relief through O2 generation and cellular glutathione (GSH) consumption, compared to the OH radical generation potential of Mn2+. The gelation time-controlled, catheter-injectable, and rheologically tuned multitherapeutic/embolic gel system effectively reaches distal arterioles, ensuring complete intravascular casting with fewer complications related to organic solvents. Glucose deprivation, cascade reactive oxygen species (ROS) generation, GSH depletion, and sustained release profiles of multiple drug cargos from the hydrogel system are also achieved. The combined chemo/starvation/chemodynamic efficacies of these designed hydrogel systems are confirmed in HCC cell cultures and HCC-bearing animal models. The developed radiopaque/injectable/embolic/sol-to-gel transformable systems for TACSCE therapy may offer enhanced therapeutic efficacies compared to typical transarterial embolization and transarterial chemoembolization procedures for HCC.

NOx generation in marine dual-fuel engines: Effects of ammonia blending ratio and spark ignition timing

Ammonia application in marine engines can effectively mitigate greenhouse gas emissions. However, engines powered by ammonia produce considerably higher levels of NOx emissions compared to conventional fuel engines. In the present study, a combustion model for the marine dual-fuel engine fueled with natural gas and ammonia has been established using the CONVERGE software. The nitrogen element-tracking method is employed in the engine combustion simulation. This study aims to investigate the effects of ammonia blending ratio (XNH3 = 0% ∼ 50%) and spark ignition timing (SIT = −20 °CA ATDC ∼ −40 °CA ATDC) on the emission characteristics and spatiotemporal distribution of nitrogen-based pollutants under lean-burn and stoichiometric-burn conditions. The results indicate that as the XNH3 increases, total NOx emissions decrease at stoichiometric-burn conditions, while it initially increases and then decreases at lean-burn conditions, reaching a peak of 3760 ppm at XNH3 = 30%. Besides, fuel NO emissions are predominant at lean-burn conditions, whereas at stoichiometric-burn conditions, thermal N*O emissions are predominant. Additionally, as the SIT advances, total NOx emissions initially decrease and then remain unchanged, reaching a minimum at −35 °CA ATDC, and it gradually increases at lean-burn combustions. Furthermore, the spatial distribution of NO at CA50 illustrates that fuel NO is primarily concentrated at the flame front, while thermal N*O predominates in the high-temperature burned region. N2O is observed in the low-temperature region near the cylinder wall during the expansion stroke. Moreover, fuel NO is primarily produced by ammonia's decomposition with OH radicals. There are three dominant reactions for the formation of NO: HNO→NO, NH→NO, and N→NO. The coupling mechanism of carbon and nitrogen elements is achieved by H2CN and HCN radicals.