O2 System Research Articles

Reaction mechanism of pyridine radicals with molecular oxygen: A theoretical study

Pyridine is a suitable surrogate of the fuel-nitrogen in flame studies. The goal of the present work was to extend the analysis of reactions of pyridyl radicals with O2. All reactions proceed following similar mechanisms, through the barrier-free addition of an O2 molecule and further development along two main paths: through barrier-free abstraction of an oxygen atom and through the formation of a seven-membered ring. The energies of the main intermediates of all three reactions, calculated relative to the pyridyl + O2 system, have similar values. All three reactions are characterized by the formation of 1λ2-pyrrole, as well as HCO, HCN, C2H2 and CO.

Rapid Size Determination of Quasispherical Gold Nanoparticles by Electrocatalysis Efficiency-Regulated Electrochemiluminescence.

The size of gold nanoparticles (AuNPs) largely decides their properties and applications, making the rapid screening of AuNP size important. Despite the fact that AuNP-amplified electrochemiluminescence (ECL) is widely used in various ECL sensing applications, the mechanism of ECL enhancement remains elusive, especially the quantitative relationship between the enhanced ECL intensity and the size of AuNPs. In this work, taking quasispherical and citrate-stabilized AuNPs as model nanoparticles, we have reported that the ECL intensity of the S2O82--O2 system enhanced significantly with the increasing AuNP size. AuNPs acted as bielectrocatalysts for reducing the S2O82- and O2. The further study of enhancement mechanism demonstrates that AuNPs with increasing size facilitate the electron transfer and promote the generation of radicals required for the ECL emission, which produces more emitters-singlet oxygen. Meanwhile, the high surface density of citrate on small AuNPs suppresses the ECL signal by forming an electrostatic barrier. On the basis of the above phenomena, an ECL-based rapid AuNP size screening approach has been established. The accuracy of this platform is verified by the consistent results in comparison to transmission electron microscopy (TEM) measurements. This work not only provides deep insight into the correlation between the AuNP size and the ECL enhancement but also contributes an alternative to the TEM technique for the rapid AuNP size screening. Additionally, this study also extends the exploration of ECL-based structure analysis techniques toward nanomaterials through clarifying the structure-electrocatalytic activity correlation.

Comparison of the developmental competence of in vitro-produced mouse embryos cultured under 5 versus 2% O2 with in vivo-derived blastocysts.

The prevalence of infertility in Canada has substantially increased over 30 years, and plateaued success rates of culture systems warrant further optimization for transfer outcomes. In clinical programs, embryos commonly undergo extended culture under 5% O2 until the blastocyst stage. The aim of this study is to characterize the developmental competence and stress-related responses of embryos cultured under 5 versus 2% O2 in comparison to in vivo-derived blastocysts. We hypothesized 2% O2 compromises developmental competence through altered embryonic stress responses and induction of apoptosis-related genes relative to those cultured under 5% O2 and in vivo-derived blastocysts. Quantitative measures of development and relative expressions of a cohort of stress-related genes in CD1 mouse zygotes cultured to blastocysts under 5 or 2% O2 were compared to in vivo-derived embryos. Apoptotic responses were evaluated using an immunofluorescence assay for Caspase-3. The mean percentage of blastocysts developed, and total cell number of embryos derived in vivo or cultured under 5% O2 was significantly higher than those cultured under 2% O2. Blastocyst expansion was greatest in embryos cultured under 5% O2. Stress response genes were significantly upregulated in embryos cultured under 2% O2, and expression of antioxidant-related genes was significantly lower in cultured versus in vivo-derived embryos. Caspase-3 immunofluorescence was significantly higher in cultured embryos versus in vivo-derived embryos. We inferred that 5% O2 systems better approximate physiologic oxygen availability for culture of mouse embryos, warranting re-evaluation of culturing embryos under threshold or sub-physiologic oxygen concentrations during clinical IVF programs.

Rational design of the temperature-responsive nonflammable electrolyte for safe lithium-ion batteries

The development of nonflammable electrolytes is critical for breaking the trade-off between the safety and energy density in Li-ion batteries (LIBs). Here, a rational design strategy of temperature-responsive nonflammable electrolytes (TRNEs) is proposed which are capable to prevent the heat accumulation and extinguish the fire efficiently during thermal runaway. Compared to the conventional phosphate- or halogen-based flame retardants, the TRNE based on low-cost and multifunctional methylurea (MU) was demonstrated with the lowest volatility (11.6 % weight loss) below 250 °C, and the highest efficacy to extinguish the fire at >210.4 °C through heat absorption, inert gases generation and char layer formation. In addition, the developed MU-based TRNEs enable higher stability and rate capability of LIBs compared to various nonflammable electrolytes. A Li||LiFePO4 (LFP) cell employing MU-based TRNE achieved higher stability (94.9 % capacity retention for 1500 cycles) than commercial electrolyte. A Ni-rich Li||LiNi0.8Mn0.1Co0.1O2 (NMC811) system was demonstrated with superior rate capability and high stability for 700 cycles (2.72 months) with the capacity retention of 89.9 %. Combining low cost and volatility, as well as high stability, rate capability and fire extinguishing efficacy, we demonstrate a promising design strategy to improve the battery safety for high-energy-density LIBs.

Suppression effect of CO2 on ignition and combustion of AlH3-nanoparticles: A molecular dynamics study

AlH3 is a high-capacity hydrogen storage material but is prone to explosion. Thermodynamic and structural properties of AlH3-nanoparticles at different CO2 inerting systems from ignition to combustion are studied using ReaxFF-MD method. The influence of CO2 on AlH3-nanoparticles ignition and combustion is investigated by comparing the changes of surface O adsorption rates, particle charge, temperature rise rates and so on. Results indicate that an increase in CO2 is crucial for suppressing AlH3-nanoparticles ignition and combustion by impeding the formation of an Al-rich environment. In contrast to three stages of AlH3-nanoparticles combustion in pure O2 system: surface combustion, slow temperature rise, and self-sustaining combustion, the process of CO2 inerting system is different, with third stage is slow temperature rise at a constant rate. When CO2 concentration reaches to 90%, the dehydrogenation rate reduces by 70.0%, the temperature rise rate decreases by 78.6%, and the ignition delay time reaches 45 ps.

Strongly active and environmentally friendly WO3/C3N4 photocatalysts for converting cyclohexane to cyclohexanone under ambient conditions

C–H bond activation under mild conditions remains a great challenge in the chemical industry, while catalytic cyclohexane oxidation is inefficient and often requires organic solvents and strong oxidants. This study constructed a C3N4/WO3 Z-type heterojunction catalyst to efficiently convert cyclohexane into cyclohexanone and cyclohexanol (KA oil) through aqueous phase oxidation by O2 under visible light irradiation. With strong redox performance and high photogenerated carrier separation ability, the proposed composite catalyst can produce the key active species for cyclohexane oxidation in the H2O–O2 system. The reaction mechanism was clarified through experiment and DFT theory calculation. Cyclohexane was converted into cyclohexyl radical under the action of ·OH, and ·O2− converted most products into cyclohexanone. The catalyst can be recycled under optimized process conditions while reaching a KA oil yield of 139.73 μmol g−1 h−1 and a selectivity of 93.1%.

A Study on the Efficient Degradation of Sulfur Hexafluoride by Pulsed Dielectric Barrier Discharge Synergistic Active Gas

SF6 is a strong greenhouse effect gas, which is widely used in high-voltage electrical equipment such as circuit breakers and high-voltage switchgear because of its excellent insulation performance and arc extinguishing ability. In recent years, the use and emission of SF6 have been rising, and with the proposal of the dual carbon strategic goal, its harmless degradation has become an urgent problem to be solved. In this paper, SF6 was degraded by pulsed DBD plasma technology and O2. Studies have shown that the addition of O2 can effectively promote the degradation of SF6. With the increase in the added O2 content, the DRE and EY of SF6 first increased and then decreased. Under the conditions of the input power of 50 W, SF6 concentration of 2%, and gas flow rate of 50 mL/min, the reaction system obtained the highest DRE and EY of 58.40% and 5.24 g/kWh when the O2 content was 1%, respectively. In the SF6/Ar/O2/H2O system, the addition of H2O could improve the product selectivity of SO2F2, and when the O2 concentration was 1%, the highest selectivity of SO2F2 was 48.96%, and the concentration was 8006.76 ppm. The addition of O2 inhibited the production of SO2, and with the addition of the O2 system, SO2F2 and SOF4 were the main components of degradation products; however, there were also SOF2, SO2, SiF4, SF4, etc. In this paper, the decomposition path of O2 under SF6 was analyzed in detail according to infrared spectroscopy and decomposition products.

Silica Nanochannels as Nanoreactors for the Confined Synthesis of Ag NPs to Boost Electrochemical Stripping Chemiluminescence of the Luminol-O2 System for the Sensitive Aptasensor.

Herein, we, for the first time, synthesize silver nanoparticles (Ag NPs) within the nanochannels of amino group-functionalized vertically ordered mesoporous silica films (NH2-VMSF) and investigate their coreaction accelerator role in the luminol-dissolved oxygen (O2) electrochemical stripping chemiluminescence (ESCL) system. The synthesized Ag NPs are capable of electrocatalytic reduction of O2 to superoxide radicals, and meanwhile, sliver ions (Ag+) electrochemically stripped from Ag NPs can promote the amount of luminol anion radicals, generating the boosted ECL intensity of the luminol-dissolved O2 system. This proposed Ag NPs@NH2-VMSF on the indium tin oxide electrode was applied to construct the ESCL aptasensor for quantitative determination of prostate-specific antigen (PSA), yielding a low detection limit [0.19 pg/mL (S/N = 3)] and a broad linear dynamic range (1 pg/mL to 100 ng/mL). Furthermore, good analytical performance of PSA in serum with satisfactory recoveries and low relative standard deviation values is achieved by our developed ESCL aptasensor, rendering it a convenient and sensitive method for PSA determination in clinical applications and further broadening the strategy of ESCL techniques.

Global Potential Energy Surfaces by Compressed-State Multistate Pair-Density Functional Theory for Hyperthermal Collisions in the O2+O2 System.

Interactions between oxygen molecules play an important role in atmospheric chemistry and hypersonic flow chemistry in atmospheric entries. Recently, high-quality ab initio potential energy surface (PES) of the quintet O4 was reported by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. 10543 configurations were sampled and calculated at the level of MS-CASPT2/maug-cc-pVTZ with scaled external correlation. The PES was fitted to a many-body (MB) form with the many-body part described by the permutationally invariant polynomial approach (MB-PIP). In this work, the PIP-Neural Network (PIP-NN) and MB-PIP-NN methods were used to refit the PES based on the same data by Paukku et al. Three PESs were compared. It was found that the performances differ significantly in the O+O3 region as well as in the long-range region. Therefore, additional 1300 points were sampled, and the efficient compressed-state multistate pair-density functional theory (CMS-PDFT) was used to calculate the electronic structure of these 1300 points and 10543 points by Paukku et al. Then, a completely new quintet PES was fitted using the MB-PIP-NN method. Based on this PES, the quasi-classical trajectory (QCT) approach was used to reveal all possible reaction channels for hyperthermal O2-O2 collisions.

Generating Concentration Gradients across Membranes for Molecular Dynamics Simulations of Periodic Systems.

The plasma membrane forms the boundary between a living entity and its environment and acts as a barrier to permeation and flow of substances. Several computational means of calculating permeability have been implemented for molecular dynamics (MD) simulations-based approaches. Except for double bilayer systems, most permeability studies have been performed under equilibrium conditions, in large part due to the challenges associated with creating concentration gradients in simulations utilizing periodic boundary conditions. To enhance the scientific understanding of permeation and complement the existing computational means of characterizing membrane permeability, we developed a non-equilibrium method that enables the generation and maintenance of steady-state gradients in MD simulations. We utilize PBCs advantageously by imposing a directional bias to the motion of permeants so that their crossing of the boundary replenishes the gradient, like a previous study on ions. Under these conditions, a net flow of permeants across membranes may be observed to determine bulk permeability by a direct application of J=PΔc. In the present study, we explore the results of its application to an exemplary O2 and POPC bilayer system, demonstrating accurate and precise permeability measurements. In addition, we illustrate the impact of permeant concentration and the choice of thermostat on the permeability. Moreover, we demonstrate that energetics of permeation can be closely examined by the dissipation of the gradient across the membrane to gain nuanced insights into the thermodynamics of permeability.

Exogenous Co-Reactant-Free Electrochemiluminescent Biosensor for Ratiometric Measurement of α-Glucosidase Based on a ZIF-67-Regulated Hydrogen-Bonded Organic Framework.

The development of highly sensitive and selective analytical approaches for monitoring enzymatic activity is critical for disease diagnosis and biomedical research. Herein, we develop an exogenous co-reactant-free electrochemiluminescence (ECL) biosensor for the ratiometric measurement of α-glucosidase (α-Glu) based on a zeolitic imidazolate framework (ZIF-67)-regulated pyrene-based hydrogen-bonded organic framework (HOF-101). Target α-Glu can hydrolyze maltose to α-d-glucose, which can subsequently react with GOx to produce gluconic acid. The resultant gluconic acid can dissolve ZIF-67, leading to the recovery of the HOF-101 cathodic ECL signal and the decrease of the luminol anodic ECL signal. The long-range ordered structure of HOF-101 can speed up charge transfer, resulting in a stable and strong cathodic ECL signal. Moreover, ZIF-67 can not only efficiently quench the ECL signal of HOF-101 due to ECL resonance energy transfer between HOF-101 and ZIF-67 as well as the steric hindrance effect of ZIF-67 but also enhance the anodic ECL emission of luminol in dissolved O2 system because of its ordered and porous crystalline structure and the atomically dispersed Co2+. Notably, HOF-101 possesses a higher ECL efficiency (32.22%) compared with the Ru(bpy)32+ standard. Importantly, this ratiometric ECL biosensor shows high sensitivity (a detection limit of 0.19 U L-1) and a broad linear range (0.2-50 U L-1). This biosensor can efficiently eliminate systematic errors and enhance detection reliability without the involvement of exogenous co-reactants, and it displays good assay performance in human serum samples, holding great promise in biomedical research studies.

Multivalent copper nanospheres with efficient molecular oxygen activation to remarkably enhance electrochemiluminescence of luminol/dissolved O2 system for biosensing assay

Herein, multivalent copper nanospheres (Cu NSs) with efficient molecular oxygen activation are presented as a novel co-reaction accelerator in the luminol/dissolved O2 electrochemiluminescence (ECL) system. This advancement significantly enhances ECL emission, combined with a highly efficient target conversion cascade amplification strategy to construct a “signal-on” type ultrasensitive biosensor for microRNA-21 (miRNA-21) detection. Intriguingly, the multivalent Cu NSs as co-reaction accelerators expedite the activation of dissolved O2, generating reactive oxide species (ROS) without electro-excitation. This process markedly boosts the ECL intensity, thereby improving detection sensitivity. In addition, incorporating a target conversion cascade amplification strategy enables the conversion of trace amounts of target miRNA-21 into abundant mimic targets. These mimic targets then assemble into a dendritic DNA nanostructure, facilitating the efficient immobilization of a copious amount of the ECL emitter, doxorubicin-luminol (Dox-Lum), further enhancing the sensitivity of the biosensor. Consequently, the developed biosensor achieves highly sensitive detection of miRNA-21, demonstrating a low detection limit of 59 aM. It was preliminarily applied to determine miRNA-21 in lysates from tumor cells. This strategy introduces a negative voltage-free co-reaction accelerator, significantly amplifying the ECL signal in a ternary ECL system, and offers a promising analytical method for early clinical diagnosis.

Enhancing Photosynthesis Efficiency of Hydrogen Peroxide by Modulating Side Chains to Facilitate Water Oxidation at Low-Energy Barrier Sites.

Hydrogen peroxide (H2O2) is a crucial oxidant in advanced oxidation processes. In situ, photosynthesis of it in natural water holds the promise of practical application for water remediation. However, current photosynthesis of H2O2 systems primarily relies on oxygen reduction, leading to limited performance in natural water with low dissolved oxygen or anaerobic conditions found in polluted water. Herein, a novel photocatalyst based on conjugated polymers with alternating electron donor-acceptor structures and electron-withdrawing side chains on electron donors is introduced. Specifically, carbazole functions as the electron donor, triazine serves as the electron acceptor, and cyano acts as the electron-withdrawing side chain. Notably, the photocatalyst exhibits a remarkable solar-to-chemical conversion of 0.64%, the highest reported in natural water. Furthermore, even in anaerobic conditions, it achieves an impressive H2O2 photosynthetic efficiency of 1365µmolg-1h-1, surpassing all the reported photosynthetic systems of H2O2. This remarkable improvement is attributed to the effective relocation of the water oxidation active site from a high-energy carbazole to a low-energy acetylene site mediated by the side chains, resulting in enhanced O2 or H2O2 generation from water. This breakthrough offers a new avenue for efficient water remediation using advanced oxidation technologies in oxygen-limited environments, holding significant implications for environmental restoration.

Solar-powered O2 delivery for the treatment of children with hypoxaemia in Uganda: a stepped-wedge, cluster randomised controlled trial

Supplemental O2 is not always available at health facilities in low-income and middle-income countries (LMICs). Solar-powered O2 delivery can overcome gaps in O2 access, generating O2 independent of grid electricity. We hypothesized that installation of solar-powered O2 systems on the paediatrics ward of rural Ugandan hospitals would lead to a reduction in mortality among hypoxaemic children. In this pragmatic, country-wide, stepped-wedge, cluster randomised controlled trial, solar-powered O2 systems (ie, photovoltaic cells, battery bank, and O2 concentrator) were sequentially installed at 20 rural health facilities in Uganda. Sites were selected for inclusion based on the following criteria: District Hospital or Health Centre IV with paediatric inpatient services; supplemental O2 on the paediatric ward was not available or was unreliable; and adequate space to install solar panels, a battery bank, and electrical wiring. Allocation concealment was achieved for sites up to 2 weeks before installation, but the study was not masked overall. Children younger than 5 years admitted to hospital with hypoxaemia and respiratory signs were included. The primary outcome was mortality within 48 h of detection of hypoxaemia. The statistical analysis used a linear mixed effects logistic regression model accounting for cluster as random effect and calendar time as fixed effect. The trial is registered at ClinicalTrials.gov, NCT03851783. Between June 28, 2019, and Nov 30, 2021, 2409 children were enrolled across 20 hospitals and, after exclusions, 2405 children were analysed. 964 children were enrolled before site randomisation and 1441 children were enrolled after site randomisation (intention to treat). There were 104 deaths, 91 of which occurred within 48 h of detection of hypoxaemia. The 48 h mortality was 49 (5·1%) of 964 children before randomisation and 42 (2·9%) of 1440 (one individual did not have vital status documented at 48 h) after randomisation (adjusted odds ratio 0·50, 95% CI 0·27-0·91, p=0·023). Results were sensitive to alternative parameterisations of the secular trend. There was a relative risk reduction of 48·7% (95% CI 8·5-71·5), and a number needed to treat with solar-powered O2 of 45 (95% CI 28-230) to save one life. Use of O2 increased from 484 (50·2%) of 964 children before randomisation to 1424 (98·8%) of 1441 children after randomisation (p<0·0001). Adverse events were similar before and after randomisation and were not considered to be related to the intervention. The estimated cost-effectiveness was US$25 (6-505) per disability-adjusted life-year saved. This stepped-wedge, cluster randomised controlled trial shows the mortality benefit of improving O2 access with solar-powered O2. This study could serve as a model for scale-up of solar-powered O2 as one solution to O2 insecurity in LMICs. Grand Challenges Canada and The Women and Children's Health Research Institute.

Ultralow operating voltage for energy conversion performance in Hf1–xZrxO2 thin films

Emerging ferroelectric and antiferroelectric HfO2-based thin films are attractive candidates for energy conversion and storage applications. In this work, the polar phase transformation between tetragonal and orthorhombic phases associated with ferroelectric or antiferroelectric behaviors is utilized to manipulate the electrocaloric cooling and energy storage performances in Zr-doped, woken up HfO2 ultrathin films. A giant electrocaloric temperature change of up to 11.85 K in Hf0.5Zr0.5O2 with the morphotropic phase boundary (MPB) state and a high energy storage density of 39.34 J/cm3 in the tetragonal phase-dominant Hf0.25Zr0.75O2 system are obtained. More interestingly, contrary to overdoping and excessive electric fields, an appropriate Zr concentration of 0.5 and an applicable driving field of 1.91 MV/cm are desired for the electrocaloric effect, resulting in an ultralow operating voltage as low as 1.3 V in this 6.8 nm thick Hf0.5Zr0.5O2 film. These findings illustrate that the structural design strategy is a visible method for achieving optimal energy-related behaviors and highlight the great possibilities for building future energy-related devices.

Phosphonates-enhanced production of reactive oxygen species by ferrous ion in the presence of oxygen: Effects and mechanisms

Due to their potential environmental hazards, the ongoing release of phosphonates into natural water bodies has sparked serious worries. Phosphonates are typically found as metal-phosphonate complexes in natural water and their complex with Fe2+ is predominant. In this study, we demonstrated that phosphonates could enhance reactive oxygen species (ROS) production upon complexation with Fe2+ in the presence of O2 (from the air). Using aminotris (methyphosphonic acid) (ATMP) as a model phosphonate, we thoroughly investigated the effects and mechanism of ROS production in the ATMP/Fe2+/O2 system. OH•-mediated oxidation was responsible for the transformation of co-existing contaminants. With oxygen (O-) and nitrogen (N-) in ATMP complexed with Fe2+, the redox potential of Fe2+/Fe3+ was significantly reduced, thus promoting OH• production. Further experiments identified OH• production followed the one-electron transfer pathway (O2 → O2•- → H2O2 → OH•). Due to the generation of OH•, 61.5% of phenol (10 mg/L) was degraded and a small fraction of ATMP underwent C-P bond cleavage. The phenomenon of ATMP-enhanced ROS production and co-existing pollutants degradation occurred throughout a wide pH spectrum from 3.0 to 10.0. This study not only clarified how ROS were produced in the ATMP/Fe2+/O2 system, but also provided new ideas for understanding the environmental behavior of phosphonates in promoting co-existing pollutants degradation.

Single iron atom embedded in dual-size nitrogen-doped carbon framework on reduced graphene oxide: An effective catalyst for proton exchange membrane fuel cells

The commercialization of Proton Exchange Membrane Fuel Cells (PEMFCs) is hindering by the cost of noble metal catalysts. We are introducing A-FeSAC-NCDS/rGO, a novel catalyst derived from metal-organic framework through carbonization and ammonia treatment. This catalyst is incorporating single iron atoms (FeSAC) within dual-sized porous nitrogen-carbon frameworks (NCDS, 30 nm and 100 nm), supporting on reduced graphene oxide (rGO). The catalyst is providing abundant active sites, with NCDS increasing active site density and rGO enhancing material conductivity. Consequently, catalyst is exceling in the oxygen reduction reaction, boasting an onset potential of 0.807 V and a half-wave potential of 0.779 V, near benchmark Pt/C catalyst. PEMFC tests employing A-FeSAC-NCDS/rGO achieved a power density of 780.7 mWcm−2 at 1.6 A cm−2 in an H2–O2 system. In durability tests at 0.6 Acm−2 in H2-air, voltage loss was 28.68 % after 50 h. These results position the catalyst as a promising choice for PEMFC.

Multi-Enzyme Activity of MIL-101 (Fe)-Derived Cascade Nano-Enzymes for Antitumor and Antimicrobial Therapy.

The clinical application of oncology therapy is hampered by high glutathione concentrations, hypoxia, and inefficient activation of cell death mechanisms in cancer cells. In this study, Fe and Mo bimetallic sulfide nanomaterial (FeS2@MoS2) based on metal-organic framework structure is rationally prepared with peroxidase (POD)-, catalase (CAT)-, superoxide dismutase (SOD)-like activities and glutathione depletion ability, which can confer versatility for treating tumors and mending wounds. In the lesion area, FeS2@MoS2 with SOD-like activity can facilitate the transformation of superoxide anions (O2 -) to hydrogen peroxide (H2O2), and then the resulting H2O2 serves as a substrate for the Fenton reaction with FMS to produce highly toxic hydroxyl radicals (∙OH). Simultaneously, FeS2@MoS2 has an ability to deplete glutathione (GSH) and catalyze the decomposition of nicotinamide adenine dinucleotide phosphate (NADPH) to curb the regeneration of GSH from the source. Thus it can realize effective tumor elimination through synergistic apoptosis-ferroptosis strategy. Based on the alteration of the H2O2 system, free radical production, glutathione depletion and the alleviation of hypoxia in the tumor microenvironment, FeS2@MoS2 NPS can not only significantly inhibit tumors in vivo and in vitro, but also inhibit multidrug-resistant bacteria and hasten wound healing. It may open the door to the development of cascade nanoplatforms for effective tumor treatment and overcoming wound infection.

Bifunctional TEMPO-based catalysis boosts luminol electrochemiluminescence for cholesterol sensing

Electrochemiluminesence (ECL) of luminol has been enhanced through the catalysis of various artificial nanomaterials to improve its performance in sensing applications. Herein, we report on a biofunctional-catalytic approach based on a simple organic radical, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), which enhances significantly the ECL emission for both luminol/O2 and luminol/H2O2 systems. The electrochemical studies showed that TEMPO could be oxidized to highly stable oxoammonium cation (TEMPO+) without any interferences of dissolved O2, but was found to improve the oxidation of luminol. On the other hand, TEMPO as an electrocatalyst could make the oxidation of H2O2 more efficient. This bifunctional-catalysis of TEMPO has facilitated the production of L−• in luminol/dissolved O2 system and O2−• in luminol/H2O2 system for ECL generation. Based on the enhanced ECL of luminol/TEMPO/cholesterol oxidase (ChOx)/cholesterol system, an ECL sensor has been designed for the selective and sensitive detection of cholesterol with a linear range between 0.30 μM and 100 μM and a low detection limit of 0.08 μM. Finally, the present work opens new avenues for studying luminol ECL using the bifunctional-catalysis of nitroxyl radicals.

Metagenomic Insight Reveals the Microbial Structure and Function of the Full-Scale Coking Wastewater Treatment System: Gene-Based Nitrogen Removal

Microbial communities play crucial roles in pollutant removal and system stability in biological systems for coking wastewater (CWW) treatment, but a comprehensive understanding of their structure and functions is still lacking. A five month survey of four sequential bioreactors, anoxic 1/oxic 1/anoxic 2/oxic 2 (A1/O1/A2/O2), was carried out in a full-scale CWW treatment system in China to elucidate operational performance and microbial ecology. The results showed that A1/O1/A2/O2 had excellent and stable performance for nitrogen removal. Both total nitrogen (TN; (17.38 ± 6.89) mg·L−1) and ammonium–nitrogen (NH4+-N; (2.10 ± 1.34) mg·L−1) in the final biological effluent satisfied the Chinese national standards for CWW. Integrated analysis of 16S ribosome RNA (rRNA) sequencing and metagenomic sequencing showed that the bacterial communities and metagenomic function profiles of A1 and O1 shared similar functional structures, while those of A2 significantly varied from those of other bioreactors (p < 0.05). The results indicated that microbial activity was strongly connected with activated sludge function. Nitrosospira, Nitrosomonas, and SM1A02 were responsible for nitrification during the primary anoxic–oxic (AO) stage and Azoarcus and Thauera acted as important denitrifiers in A2. Nitrogen cycling-related enzymes and genes work in the A1/O1/A2/O2 system. Moreover, the hao genes catalyzing hydroxylamine dehydrogenase (EC 1.7.2.6) and the napA and napB genes catalyzing nitrate reductase (EC 1.9.6.1) played important roles in the nitrification and denitrification processes in the primary and secondary AO stages, respectively. The mixed liquor suspended solids (MLSS)/total solids (TS), TN removal rate (RR), total organic carbon (TOC) (RR), and NH4+-N (RR) were the most important environmental factors for regulating the structure of core bacterial genera and nitrogen-cycling genes. Proteobacteria were the potential main participants in nitrogen metabolism in the A1/O1/A2/O2 system for CWW treatment. This study provides an original and comprehensive understanding of the microbial community and functions at the gene level, which is crucial for the efficient and stable operation of the full-scale biological process for CWW treatment.