Oxidation Products Research Articles

Oxidative stress-mediated neuroinflammation in Alzheimer's disease.

Reactive oxygen species (ROS) are metabolic by-products that constitute an indispensable component of physiological processes, albeit their heightened presence may proffer substantial perils to biological entities. Such a proliferation gives rise to a gradual escalation of oxidative stress within the organism, thereby compromising mitochondrial functionality and inflicting harm upon various bodily systems, with a particular predilection for the central nervous system. In its nascent stages, it is plausible that inflammation has been a facilitator in the progression of the malady. The precise role of inflammation in Alzheimer's disease (AD) remains somewhat enigmatic, although it is conceivable that activated microglia and astrocytes might be implicated in the removal of amyloid-β (Aβ) deposits. Nonetheless, prolonged microglial activation is associated with Tau phosphorylation and Aβ aggregation. Research studies have indicated that AD brains upregulate complementary molecules, inflammatory cytokines, acute phase reacting agents, and other inflammatory mediators that may cause neurodegeneration. In this review, oxidative damage products will be discussed as potential peripheral biomarkers for AD and its early stages. The disordered excretion of pro-inflammatory cytokines, chemokines, oxygen, and nitrogen-reactive species, along with the stimulation of the complement system by glial cells, has the potential to disrupt the functionality of neuronal termini. This perturbation, in turn, culminates in compromised synaptic function, a phenomenon empirically linked to the manifestation of cognitive impairments. The management of neurodegenerative conditions in the context of dementia necessitates therapeutic interventions that specifically target the excessive production of inflammatory and oxidative agents. Furthermore, we shall deliberate upon the function of microglia and oxidative injury in the etiology of AD and the ensuing neurodegenerative processes.

Colorimetric array sensor based on bimetallic nitrogen-doped carbon-based nanozyme material to detect multiple antioxidants.

Copper-cobalt bimetallic nitrogen-doped carbon-based nanoenzymatic materials (CuCo@NC) were synthesized using a one-step pyrolysis process. A three-channel colorimetric sensor array was constructed for the detection of seven antioxidants, including cysteine (Cys), uric acid (UA), tea polyphenols (TP), lysine (Lys), ascorbic acid (AA), glutathione (GSH), and dopamine (DA). CuCo@NC with peroxidase activity was used to catalyze the oxidation of TMB by H2O2 at three different ratios of metal sites. The ability of various antioxidants to reduce the oxidation products of TMB (ox TMB) varied, leading to distinct absorbance changes. Linear discriminant analysis (LDA) results showed that the sensor array was capable of detecting seven antioxidants in buffer and serum samples. It could successfully discriminate antioxidants with a minimum concentration of 10nM. Thus, multifunctional sensor arrays based on CuCo@NC bimetallic nanoenzymes not only offer a promising strategy for identifying various antioxidants but also expand their applications in medical diagnostics and environmental analysis of food.

Plant acclimation to ionising radiation requires activation of a detoxification pathway against carbonyl-containing lipid oxidation products.

Ionising γ radiation produces reactive oxygen species by water radiolysis, providing an interesting model approach for studying oxidative stress in plants. Three-week old plants of Arabidopsis thaliana were exposed to a low dose rate (25 mGy h-1) of γ radiation for up to 21 days. This treatment had no effect on plant growth and morphology, but it induced chronic oxidation of lipids which was associated with an accumulation of reactive carbonyl species (RCS). However, contrary to lipid peroxidation, lipid RCS accumulation was transient only, being maximal after 1 day of irradiation and decreasing back to the initial level during the subsequent days of continuous irradiation. This indicates the induction of a carbonyl-metabolising process during chronic ionising radiation. Accordingly, the γ-radiation treatment induced the expression of xenobiotic detoxification-related genes (AER, SDR1, SDR3, ALDH4, and ANAC102). The transcriptomic response of some of those genes (AER, SDR1, and ANAC102) was deregulated in the tga256 mutant affected in three TGAII transcription factors, leading to enhanced and/or prolonged accumulation of RCS and to a marked inhibition of plant growth during irradiation compared to the wild type. These results show that Arabidopsis is able to acclimate to chronic oxidative stress and that this phenomenon requires activation of a carbonyl detoxification mechanism controlled by TGAII. This acclimation did not occur when plants were exposed to an acute γ radiation stress (100 Gy) which led to persistent accumulation of RCS and marked inhibition of plant growth. This study shows the role of secondary products of lipid peroxidation in the detrimental effects of reactive oxygen species.

A portable microfluidic electrochemical sensor with nonlinear fit strategy for wide-range uric acid detection

In this work, we have developed a portable electrochemical sensing device controlled by a smartphone through Bluetooth, which was applied for regular uric acid (UA) monitoring in prevention and healthcare management. On the core lies a nonlinear fitting model (I = k·(N − exp(−K·cbulk + b))) which is proposed for the first time and given from the differential equation based on the theoretical analysis. We believe this model can reflect the intrinsic relationship between the obtained current and the bulk analyte concentration, therefore leading to an expanding UA detection range (10-fold) compared to the widely used linear standard curve model and reducing the requirements for the modification of the electrode materials. Besides, the integration of the microfluidic chip promoted the removal of UA oxidation products at the electrode surface, yielding excellent sensing stability with a relative standard deviation (RSD) lower than 1 % during 10 consecutive runs. Consequently, we acquired the relationship between Square Wave Voltammetry (SWV) current and UA concentration (I = 15.27*(2.05 − exp(−0.00108*(cbulk − 663.5))), R2 = 0.9999) in the range of 5 to 1000 μM with a limit of detection (LoD) of 2.4 μM using a completely unmodified screen-printed carbon electrode (SPCE). Proof of concept experiments using 25× diluted human urine spiked with UA yielded a recovery rate of 87.5–101.4 % and a satisfactory selectivity result, which is within the value expected for clinical use, indicating the potential of the developed instrument and nonlinear fitting model for urinary UA detection.

Synergistic Enhancement on Ignition and Combustion Properties of Boron via Viton Core-Shell Coating.

The high gravimetric (58.74 kJ/g) and volumetric (137.45 kJ/cm3) heat values loaded in boron (B) offer significant potential for application in solid propellants and explosives. However, the high melting (2076 °C) and boiling (3927 °C) points of boron powder and the low melting point (450 °C) of oxidation products affect the energy performance and application of boron. Fluorine-containing polymers have high oxidation potential and excellent mechanical properties and can produce expectant gaseous products through the combustion reaction with boron oxide, but research examining the interaction between purified boron powder and fluoropolymers and the optimal selection of the fluoropolymer remains scarce. Herein, the binding energy between typical fluoropolymers [Viton, polyvinylidene fluoride, poly(vinylidene fluoride-co-chlorotrifluoroethylene), and vinylidene fluoride] and boron was calculated via molecular dynamics simulations, which shows that Viton is an appropriate candidate for coating boron powder. In the experiment, The Bw@Viton core-shell composites were prepared using Viton as the coating layer, and boron powder was pre-purified with acetonitrile. Its structure, thermal properties, ignition, and combustion characteristics were then characterized. The results revealed successful removal of the oxide layer, and the hydrophobicity was significantly improved after Viton coating. Purification and coating synergistically enhance the energy release of boron powder, and the composites demonstrated excellent thermal, ignition, and combustion performances. In particular, the heat of oxidation and heat of combustion were increased by 26.6 and 32.7%, respectively. The ignition delay time was reduced by 53.2% compared to raw boron. A prospective reaction mechanism between boron and Viton is thus proposed.

Determination of the critical aggregation concentration in water of Gum Arabic functionalized with curcumin oxidation products by micro-scale thermophoresis approach

Gum Arabic underwent enzymatic modification with curcumin oxidation products, prompting self-assembly in water at lower concentrations than native gum Arabic, which was fully soluble. The resulting particles displayed a narrow size distribution, suggestive of a micellization mechanism akin to Critical Micellization Concentration (CMC) in surfactants or Critical Aggregation Concentration (CAC) in polymers. Accurately determining CAC is vital for utilizing polymers in molecule encapsulation, but precise measurement is challenging, requiring multiple techniques. Initially, CAC was probed via turbidity measurements, dynamic light scattering (DLS), and isothermal calorimetric titration (ITC), yielding a range of 0.0015 to 0.01 %. Micro-scale thermophoresis (MST) was then employed for the first time to define CAC more precisely, facilitated by the intrinsic fluorescence of modified gum Arabic. Using MST, CAC was pinpointed at 0.001 % (w/v), a novel approach. Furthermore, MST revealed a low EC50 value of 0.007 % (w/t) for self-assembly, signifying uniformity among GAC sub-units and assembly stability upon dilution.

Collision Oxidation Behavior of Silver Nanoparticles in Alkaline Solution.

In recent years, silver nanoparticles (Ag NPs) have been used as positive electrode material for zinc/silver batteries, and the silver oxides formed during the charging process determine the discharge performance of batteries. Therefore, it is important to study the oxidation behavior of Ag NPs in alkaline solution. Single-nanoparticle collision is an important tool for analyzing oxidation behavior of individual nanoparticles. Based on thermodynamic information from collision events, it is known that oxidation products are potential-dependent and size-dependent. Based on dynamic information, including collisional peak shapes and duration time, it was observed that the Ag NP collision oxidation process changed from stepwise oxidation to direct oxidation as the potential increased or size decreased. This work provides guidance for application of Ag NPs in zinc/silver batteries and proposed a strategy for oxidation behavior of individual NP that could be tracked in situ through an all-encompassing view of thermodynamic and dynamic information.

Molecular Mechanism of the Impact of Lipid Oxidation Products (2,4-Decadienal) on the Conformation of Grouper (Epinephelus coioides) Myofibrillar Proteins During Refrigeration and its Implications on the Overall Protein Flavor

Molecular Mechanism of the Impact of Lipid Oxidation Products (2,4-Decadienal) on the Conformation of Grouper (Epinephelus coioides) Myofibrillar Proteins During Refrigeration and its Implications on the Overall Protein Flavor

Odor-Active Compounds in Flexible Polyurethane Materials

Flexible polyurethane (PU) materials find extensive use in upholstery, mattresses, and automobiles, yet the molecular background of their odor is still inadequately understood. To address this gap, we aimed at identifying major odorants in fifteen samples representing eight common types of flexible PU materials. The volatiles isolated from the samples were subjected to activity-guided screening via gas chromatography-olfactometry. Structures were assigned by comparing odor, retention data, and mass spectra to those of authentic reference compounds. This approach led to the identification of 50 odorants, 39 of which had not previously been described in PU. The odorants belonged to a wide range of compound classes, including tertiary amines, fatty acid oxidation products, short-chain aldehydes, trioxocanes, pyrazines, aromatic hydrocarbons and heterocycles, chlorinated compounds, phenol derivatives, fragrance compounds, and nitriles. For some odorants, further insights were gained into their origins and release behavior. For example, the odorous 1,4-dimethylpiperazine had been used as a catalyst, and propanal was shown to be not only a PU odorant but also the precursor of an odor-active trioxocane. Additionally, the quantitation of acetaldehyde and propanal suggested their continuous regeneration from the samples. While the sources of other compounds still have to be clarified, the data obtained in this study could pave the way for odor reduction strategies in the production of PU materials, ultimately resulting in an improved odor and consumer experience.

Observation-constrained kinetic modeling of isoprene SOA formation in the atmosphere

Abstract. Isoprene has the largest global non-methane hydrocarbon emission, and the oxidation of isoprene plays a crucial role in the formation of secondary organic aerosol (SOA). Two primary processes are known to contribute to SOA formation from isoprene oxidation: (1) the reactive uptake of isoprene-derived epoxides on acidic or aqueous particle surfaces and (2) the absorptive gas–particle partitioning of low-volatility oxidation products. In this study, we developed a new multiphase condensed isoprene oxidation mechanism that includes these processes with key molecular intermediates and products. The new mechanism was applied to simulate isoprene gas-phase oxidation products and SOA formation from previously published chamber experiments under a variety of conditions and atmospheric observations during the Southern Oxidant and Aerosol Studies (SOAS) field campaign. Our results show that SOA formation from most of the chamber experiments is reasonably reproduced using our mechanism, except when the concentration ratios of initial nitric oxide to isoprene exceed ∼ 2, the formed SOA is significantly underpredicted. The SOAS simulations also reasonably agree with the measurements regarding the diurnal pattern and concentrations of different product categories, while the total isoprene SOA remains underestimated. The molecular compositions of the modeled SOA indicate that multifunctional low-volatility products contribute to isoprene SOA more significantly than previously thought, with a median mass contribution of ∼ 57 % to the total modeled isoprene SOA. However, this contribution is intricately intertwined with IEPOX-derived SOA (IEPOX: isoprene-derived epoxydiols), posing challenges for their differentiation using bulk aerosol composition analysis (e.g., the aerosol mass spectrometer with positive matrix factorization). Furthermore, the SOA from these pathways may vary greatly, mainly dependent on the volatility estimation and treatment of particle-phase processes (i.e., photolysis and hydrolysis). Our findings emphasize that the various pathways to produce these low-volatility species should be considered in models to more accurately predict isoprene SOA formation. The new condensed isoprene chemical mechanism can be further incorporated into regional-scale air quality models, such as the Community Multiscale Air Quality Modelling System (CMAQ), to assess isoprene SOA formation on a larger scale.

Temperature dependence mechanism of high-temperature oxidation of transition metal silicide MoSi2

Transition metal silicides represented by MoSi2 have excellent oxidation resistance and are widely used as high-temperature anti-oxidation coatings in hot end components of power equipment. However, the mechanism of temperature-dependent growth of MoSi2 oxidation products has not been revealed. Therefore, this study investigated the formation characteristics of oxide film and silicide-poor compound on MoSi2 at temperatures of 1000 °C–1550 °C through high-temperature oxidation experiments, combined with microscopic Raman spectroscopy, scanning electron microscope, and x-ray diffraction (XRD) characterizations. The result showed that MoSi2 underwent high-temperature selective oxidation reactions at 1000 °C–1200 °C, forming MoO2 and SiO2 oxide film on the substrate. As the oxidation temperature increased to 1550 °C, after 100 h of oxidation, along with the disappearance of MoO2 and the phase transformation of SiO2, a continuous Mo5Si3 layer with a thickness of approximately 47 μm was formed at the SiO2–MoSi2 interface. Thermodynamics and kinetic calculations further revealed the mechanism of temperature-dependent growth of oxidation products (MoO2 and Mo5Si3) during high-temperature oxidation process of MoSi2. As the temperature increased, the diffusion flux ratio of O and Si decreased, leading to a decrease in oxygen concentration at the interface and promoting the growth of the Mo5Si3 layer. Its thickness is an important indicator for evaluating the oxidation resistance of MoSi2 coatings during service. This study provides experimental and mechanistic insights into the temperature-dependent growth behavior of Mo5Si3 during the high-temperature oxidation of MoSi2 coating, and provides guidance for predicting the service life and improving the oxidation resistance of silicide coatings.

Stability of Liposomal Membrane of Hemoglobin-Vesicles (Artificial Red Cells) for Over Years of Storage Evaluated Using Liquid Chromatography-Mass Spectrometry.

Hemoglobin-Vesicles (Hb-V) are artificial oxygen carriers encapsulating a purified and concentrated Hb solution in liposomes composed of 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC), cholesterol, 1,5-O-dihexadecyl-N-succinyl-l-glutamate (DHSG), and 1,2-distearoyl-sn-glycero-3-phosphatidylethanolamine-N-poly(ethylene glycol) (PEG5000) (DSPE-PEG). The safety and efficacy of Hb-V have been studied extensively by both preclinical and clinical test methods. Deoxygenation of Hb-V prevents autoxidation of Hb and can extend its shelf life to 2 years at room temperature. However, the lipid components raise concerns about hydrolysis because Hb-V is dispersed in saline. For this study, we attempted to estimate the lipid degradation of long-term stored Hb-V using liquid chromatography-mass spectrometry. Analyses of lipid components extracted from the stored Hb-V showed that the degradation increased depending on the storage temperature. The calculated % remaining of intact lipids of Hb-V were 98.1% after 4 years and 90.4% after 7.2 years at 4 °C, 95.8% after 1 year and 86.7% after 2 years at 25 °C, and 85.6% after 6 months at 40 °C. The main degradation products were lyso-PC and palmitic acid which are hydrolyzed at the ester bond of DPPC. A few hydrolyzed products of DHSG and DSPE-PEG were also detected in Hb-V, but almost no degradation or oxidation products derived from cholesterol could be identified. A shear test of Hb-V at 1500 s-1 showed no significant increase in Hb leakage after storage of 2 years at 25 °C and 6 months at 40 °C. Lipid degradation products including free fatty acids would decrease the pH of the Hb-V dispersion and synergistically facilitate degradation, but it maintained pH 6.5 during 6 years at 4 °C, 2 years at 25 °C, and 3 months at 40 °C because of its high buffering capacity. These results indicate that the storage conditions for Hb-V are appropriate to minimize lipid degradation in the long term.

A Kinetic and Mechanistic Study of Ir (III)-Catalyzed Oxidation of Methionine by HCF (III) in an Aqueous Alkaline Medium

Introduction: The kinetic study of Ir (III) chloride-catalyzed oxidation of methionine by hexacyanoferrate (abbreviated as HCF) III ions in aqueous alkaline medium was performed spectrophotometrically at constant ionic strength of 0.5 moldm-3 and temperature of 35±0.10C. Method: The progress of the reaction was found to be first-order rate dependence kinetics with respect to [HCF (III)], [OH-], and [IrCl3]. The rate of reaction was found to decrease with an increased concentration of methionine. The ionic strength of the reaction mixture showed a positive salt effect on the reaction rate. Different activation parameters were also evaluated by studying the reaction at four different temperatures. The stoichiometry of the reaction showed Methionine: HCF (III) = 1:4. Result: The oxidation product of the reaction was found to be methionine sulphone, which was identified by an organic solvent method and IR Spectroscopy. Further, a suitable mechanism was proposed to explain all the experimental results. Conclusion: It is assumed that the reaction proceeded through complex formation between substrate (abbreviated) and iridium trichloride. A rate law was derived, which verified the results. CH3-S-(CH2)2-CH (NH2)-COO- + 4HCF (III) Ir (III), H2O CH3-SO2-(CH2)2-CH- (NH2)-COO- + 4HCF (II) result: 1.Methionine sulphone was found to be the main product of oxidation was identified using an organic solvent method and IR Spectroscopy. A suitable mechanism has been proposed to explain all the experimental results. It is assumed that reaction proceeds through complex formation between substrate (abbreviated) and iridium trichloride. A rate law has been derived which verifies the results. CH3 –S-(CH2)2-CH (NH2) – COO- + 4HCF (III) □(→┴(Ir(III),H2O) ) CH3-SO2-(CH2)2-CH (NH2)-COO- + 4HCF (II) 2. Degradation kinetic is anticipated to follow the first order kinetics at lower concentration. 3. The catalytic system can be recycled and reused without loss of activity. 4. The anticipated easy recovery of catalyst from the reaction mixture shows another positive signigficance.

A Comprehensive Study of Method Optimisation of Re‐Refining Spent Lubricating Oil

ABSTRACTUsed lubricating oil is generated by various machinery after extended operation. It is also referred to as spent mobile oil. Extremely hazardous waste lubricating oil is detrimental to the environment because it produces oxidative products when additives break down. Used lubricating oil is classified as a hazardous waste substance and has a negative impact on the environment. Polychlorinated biphenyls (PCBs), carcinogenic substances and other impurities make lubricating oil poisonous and pose a serious threat to human health and the environment. Re‐refining is considered the preferred technology for resource conservation, waste minimisation and reduced environmental hazards. The present study focuses on optimising the method of re‐refining waste lubricating oil. The effects of various operating parameters such as refining time, refining temperature, solvent‐to‐used oil ratio and flocculant dosage have been extensively studied to maximise the percentage recovery of lubricating oil. Optimum process parameters are (i) a refining time of 80 min, (ii) a refining temperature of 48°C, (iii) solvent‐to‐waste oil ratio of 5:1 (w/w) and (iv) a flocculant dosage of 2 g/kg of solvent; the optimum yield was found to be 75% with the solvent extraction method and 78% with the extraction–flocculation method, respectively. The purity and physico‐chemical properties of the recovered oil were thoroughly analysed using Fourier transform infrared spectroscopy and ASTM standard methods. It was concluded that refined oil can effectively reduce the ongoing oil crisis and create a clean, healthy environment.

An electrochemical sensing potential of cobalt oxide nanoparticles towards citric acid integrated with computational approach in food and biological media

Although citric acid (CA) has antioxidant, antibacterial, and acidulating properties, chronic ingestion of CA can cause urolithiasis, hypocalcemia, and duodenal cancer, emphasizing the need for early detection. There are very few documented electrochemical-based sensing methods for CA detection due to the challenging behavior of electrode fouling caused by reactive oxidation products. In this study, a novel, non-enzymatic, and economical electrochemical sensor based on cobalt oxide nanoparticles (CoOxNPs) is successfully reported for detection CA. The CoOxNPs were synthesized through a simple thermal decomposition method and characterized by SEM, FT-IR, EDX, and XRD techniques. The proposed sensing platform was optimized by various parameters, including pH (7.0), time (15 min), and concentration of nanoparticles (100 mM) etc. In a linear range of 0.05–2500 μM, a low detection limit (LOD) of 0.13 μM was achieved. Theoretical calculations (ΔRT), confirmed hydrogen bonding and electrostatic interactions between CoOxNPs and CA. The detection method exhibited high selectivity in real media like food and biological samples, with good recovery values when compared favorably to the HPLC method. To facilitate effective on-site investigation, such a sensing platform can be assembled into a portable device.

Structural characterization and bioactivities of maize bran feruloylated arabinoxylan and oligosaccharides obtained by a combined hydrothermal and enzymatic pre-treatment

Feruloylated arabinoxylans (F-AX) are gaining importance due to their immense health benefits as nutraceuticals. In the current study, we extracted F-AX from maize bran by a combination of hydrothermal pre-treatment and xylanase and cellulase double enzymatic digestion and studied them in detail. The F-AX composition included carbohydrate (533.74 ± 7.59 mg/g), and phenolic acid (153.71 ± 3.55 mg/g) with an arabinoxylan percentage of 74.17% and degree of substitution of 0.99. Ferulic acid was the major phenolic acid found esterified to arabinose. The GC, FTIR, UPLC, and methylation analysis revealed the typical structure of arabinoxylan with bound ferulic acid and a highly substituted xylopyranose backbone. The LC-MS/MS analysis revealed the structure of F-AXOS, which were the predominant oligosaccharides in the purified fraction. The F-AX showed potent antioxidant activity (DPPH, ABTS, and FRAP) and could effectively inhibit the formation of advanced glycation end products (argpyrimidine, pentosidine, and vesperlysine) and protein oxidation products (dityrosine and N′-formylkynurenine). F-AX also showed potent antiproliferative activity against the human colon cancer cells - Colo 205 and HCT 116. The current study revealed that the combined extraction method has yielded a unique blend of F-AX with bioactivities and these molecules have the potential to be used in the development of innovative functional foods.

The use of chitosan aerogels as an adsorbent for the regeneration of frying oil

One of the most commonly used food preparation methods is deep-fat frying. The improvement of the quality of used frying oil (UFO) is important because the reuse of frying oil could provide significant savings to the food industry. This study aimed to enhance the quality of used sunflower oil by using chitosan aerogels (CA), which can be considered as novel adsorbents with an increased surface area compared to chitosan powder. Aerogels are novel nanostructured materials with high porosity and large surface area. In this study, CA were produced by drying the 2% (w/v) chitosan gels using supercritical drying. In the study, 32 consecutive deep-fat frying were performed using potato slices in sunflower oil at 180 ± 5 °C. The effect of the adsorbent concentration (0.5, 1, and 2% (w/w)) and different adsorption temperatures (90, 135, and 180 °C) were studied by examining the UFO before and after the adsorption treatments. The physicochemical properties of the oil were analyzed by determining free fatty acid (FFA) content, total polar compounds (TPC), smoke point, p-anisidine value (p-AnV), and color (CIE L*, a*, b*). Moreover, the structural changes of aerogels after the adsorption process were investigated by Fourier Transform Infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR). CA could reduce the % FFA values from 0.44% to 0.18% due to the ionic interaction between CA and FFA. In addition, TPC value and the smoke point increased after the treatments. The p-AnV was compensated with CA, indicating that secondary oxidation products were adsorbed. Moreover, CA caused a darker color after the adsorption treatments. Additionally, compared with magnesium silicate, the same concentrations of CA were found more effective in improving all the quality parameters of oil except for the L* values.

Hydrogen peroxide activation and liquid‐phase selective oxidations over Ti,Zr‐based metal–organic framework PCN‐415

A mixed Ti,Zr‐based metal–organic framework, PCN‐415 (Porous Coordination Network), and the corresponding Ti,Zr‐oxocluster [Ti8Zr2O12(CH3COO)16] have been synthesized and comprehensively characterized by powder X‐Ray diffraction (PXRD), low‐temperature nitrogen adsorption, scanning electron microscopy, thermogravimetric analysis, Fourier‐transform infrared spectroscopy, and Raman spectroscopy. The catalytic performance of both PCN‐415 and the Ti,Zr‐oxocluster was evaluated in the selective oxidation of representative thioethers, alkenes, and alkylphenols using aqueous hydrogen peroxide and tert‐butyl hydroperoxide as oxidants. The nature of the oxidation products formed indicates that, most likely, both Ti and Zr sites contribute to the catalytic activity of PCN‐415, although the contribution of Ti seems to be more significant. Examination of PCN‐415 after treatment with H2O2 using diffuse reflectance UV–vis spectroscopy indicates the formation of Ti peroxo complexes while Raman spectroscopy shows evidence for the formation of both Ti and Zr peroxo species. The potential formation of missing linker‐type defects and their role in facilitating catalytic activity were addressed. The stability of the PCN‐415 structure under the catalytic conditions was confirmed by PXRD. The absence of metal leaching and the heterogeneous nature of the catalysis were verified. The catalyst could be easily recovered from the reaction mixture and reused several times without loss of the catalytic properties.

Heterogeneously Catalyzed Partial Oxidation of Styrene on a Silver Surface

AbstractThe epoxidation of olefins on Ag/O systems is a significant industrial‐scale process within heterogeneous catalysis. However, the details of the surface reaction remain controversial, and it has been highly challenging to reconcile the findings from cataltyic studies under reaction conditions with the highly detailed static studies under carefully controlled ultra‐high vacuum (UHV) conditions. In this study, we combine molecular beam surface scattering and ion imaging techniques to explore the partial oxidation of styrene. This experimental approach enhances the sensitivity to the extent that we can directly observe the partial oxidation product, styrene oxide, under UHV conditions. We note that partial oxidation exclusively occurs at high oxygen coverages, which we attribute to the reaction of styrene with electrophilic oxygen formed specifically at elevated coverages.

Natural background levels, source apportionment and health risks of potentially toxic elements in groundwater of highly urbanized area

Identifying the natural background levels (NBLs), threshold values (TVs), sources and health risks of potentially toxic elements in groundwater is crucial for ensuring the water security of residents in highly urbanized areas. In this study, 96 groundwater samples were collected in urban area of Sichuan Basin, SW China. The concentrations of potentially toxic elements (Li, Fe, Cu, Zn, Al, Pb, B, Ba and Ni) were analyzed for investigating the NBLs, TVs, sources and health risks. The potentially toxic elements followed the concentration order of Fe > Ba > B > Al > Zn > Li > Cu > Ni > Pb. The NBLs and TVs indicated the contamination of potentially toxic elements mainly occurred in the northern and central parts of the study area. The Positive Matrix Factorization (PMF) model identified elevated concentrations of Fe, Al, Li, and B were found to determine groundwater quality. The primary sources of Fe, Al, Pb, and Ni were attributed to the dissolution of oxidation products, with Fe additionally affected by anthropogenic reduction environments. Li and B were determined to be originated from the weathering of tourmaline. High levels of Ni and Cu concentrations were derived from electronic waste leakage, while excessive Ba and Zn were linked to factory emissions and tire wear. The reasonable maximum exposure (RME) of hazard index (HI) was higher than safety standard and reveal the potential health risks in the southwestern study area. Sensitivity analysis demonstrated the Li concentrations possessed the highest weight contributing to health risk. This study provides a valuable information for source-specific risk assessments of potentially toxic elements in groundwater associated with urban areas.