ABSTRACT
Metal-nitrogen (M-N) coupling has shown promise as a catalytic active component for various reactions. However, the regulation of heterogeneous catalytic materials with M-N coupling for peroxymonosulfate (PMS) activation to enhance the degradation efficiency and reusability of antibiotics remains a challenge. In this study, an efficient modulation of M-N coupling was achieved through the incorporation of Cu into Co4N to form a Cu-Co4N composite with sea urchin-like morphology assembled by numerous nano-needles using hydrothermal and nitriding processes. This modulation led to enhanced PMS activation for ciprofloxacin (CIP) degradation. The Cu-Co4N/PMS system demonstrated exceptional removal efficiency with a degradation rate of 95.85% within 30 min and can be reused for five time without obvious loss of its initial activity. Additionally, the catalyst displayed a high capacity for degrading various challenging organic pollutants, as well as remarkable stability, resistance to interferences, and adaptability to pH changes. The synergistic effect between Co and Cu facilitated multiple redox cycles, resulting in the generation of reactive oxidized species. The primary active species involved in the catalytic degradation process included 1O2, SO4â¢-, O2â¢-, â¢OH, and e-, with 1O2 and SO4â¢- playing the most significant roles. The degradation pathways and toxicity of the intermediates for CIP were unveiled. This study offers valuable insights into the regulation of M-N centers for degrading antibiotics through PMS activation.
ABSTRACT
Compared to Pt/C, the atomic ordered Pt-based intermetallic compounds can deliver higher efficiency and reliable stability, and they are considered one of the ideal cathode catalysts for the next generation of fuel cells. This work proposed a simple ferrocene atmosphere annealing method to improve commercial Pt/C and convert Pt to L10-PtFe. After further acid etching treatment, the obtained carbon-supported Pt-skin L10-PtFe (Pt-skin L10-PtFe/C) with superfine particle size (â¼3.3 nm) not only was highly dispersed on the carbon but possesses a thin Pt skin, like the armor of L10-PtFe. As excepted, the ORR activity of Pt-skin L10-PtFe/C (0.375 A mg-1; 0.921 mA cm-2) is far better than that of commercial Pt/C (0.121 A mg-1; 0.260 mA cm-2), and its stability is also greatly improved. Our proposed gas-solid reaction is straightforward and has great potential in producing Pt-based intermetallic catalysts on a large scale.
ABSTRACT
Three-dimensional sponge-architecture covalent organic frameworks (COFs)-aerogel was successfully designed and synthesized via a freeze-drying template approach, and utilized as an efficient sorbent in solid-phase extraction (SPE). A method for selective enrichment of pharmaceutical contaminants including tetracycline, chlortetracycline, methacycline and oxytetracycline in the environment and food samples was proposed by combining with high performance liquid chromatography (HPLC). To understand the adsorption mechanism, selectivity test and molecular dynamics (MD) simulated calculation were both carried out. The experimental and in-silico results demonstrated that the COFs-aerogel possessed high selectivity for contaminants with H bond acceptors/donors and good efficiency with maximum adsorption capacity up to 294.1 mg/g. The SPE-based HPLC method worked well in the range of 8-1000 ng/mL, with the need of little dose of adsorbent and sample volume while no need of spectrometer, outgoing the reported adsorbents. Under the optimized conditions, the intra-day and inter-day relative standard deviations (RSD) of repeatability were within 2.78-6.29 % and 2.44-8.42 % (n = 5). The results meet the current detection requirement for practical applications, and could be extended for further design of promising adsorbents.
Subject(s)
Anti-Bacterial Agents , Metal-Organic Frameworks , Solid Phase Extraction , Tetracyclines , Adsorption , Solid Phase Extraction/methods , Metal-Organic Frameworks/chemistry , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/analysis , Tetracyclines/analysis , Tetracyclines/chemistry , Tetracyclines/isolation & purification , Chromatography, High Pressure Liquid/methods , Molecular Dynamics Simulation , Gels/chemistry , Tetracycline/analysis , Tetracycline/chemistry , Tetracycline/isolation & purification , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Food Contamination/analysisABSTRACT
The nanoscale Cu-rich precipitates (CRPs) are one of the most critical microstructural features responsible for degrading the mechanical properties of reactor pressure vessel (RPV) steels. The prospect of the rapid regeneration of the service performance of degraded materials through electropulsing is attractive, and electropulsing has been proven to have the application potential to eliminate the CRPs and recover the mechanical properties of RPV materials. However, few studies have investigated the secondary service issue of electropulsing. This paper provides experimental findings from microstructural investigations and property evaluations of a FeCu RPV model alloy subjected to re-aging following recovery electropulsing and annealing treatments. The evolution behavior of CRPs and the changes in the hardness of the alloy during the re-aging process after electropulsing treatment were consistent with the initial aging process, while the re-aging process of the annealing treatment group was quite different from the initial aging. The difference between the electropulsing and annealing treatment groups was that the annealing treatment failed to eliminate the precipitates completely, leaving behind some large precipitates. This work demonstrates the potential application of EPT in this field.
ABSTRACT
This article applies nuclear magnetic resonance technology to the study of boron-containing traditional Chinese medicine, in order to explore the morphological evolution of boron elements in traditional Chinese medicine. Borax is a traditional Chinese medicine with anti-corrosion, anti-inflammatory, antibacterial, and anticonvulsant effects. It is made by boiling, removing stones, and drying borax minerals like borate salts. This article introduces an 11B nuclear magnetic resonance method for identifying and characterizing boron-containing compounds in TCM. We applied this technology to borax aqueous solutions in different chemical environments and found that with boron mixed in the form of SP2 hybridization in equilateral triangles and SP3 hybridization in equilateral tetrahedra, the pH changes in alkaline environments significantly affected the ratio of the two. At the same time, it was found that in addition to the raw material peak, boron signals of other boron-containing compounds were also detected in 20 commercially available boron-containing TCM preparations. These new boron-containing compounds may be true pharmaceutical active ingredients, and adding them directly to the formula can improve quality and safety. This article describes the detection of 11B NMR in boron-containing traditional Chinese medicine preparations. It is simple, non-destructive, and can provide chemical fingerprint studies for boron-containing traditional Chinese medicine.
Subject(s)
Borates , Boron , Medicine, Chinese Traditional , Magnetic Resonance SpectroscopyABSTRACT
Owing to the extremely limited structural deformation caused by the introduction of guest ions that their rigid structure can sustain, crystalline materials typically fail owing to structural collapse when utilized as electrode materials. Amorphous materials, conversely, are more resistant to volume expansion during dynamic ion transport and can introduce a lot of defects as active sites. Here, The amorphous polyaniline-coated/intercalated V2O5·nH2O (PVOH) nanowires are prepared by in situ chemical oxidation combined with self-assembly strategy, which exhibited impressive electrochemical properties because of its short-range ordered crystal structure, oxygen vacancy/defect-rich, improved electronic channels, and ionic channels. Through in situ techniques, the energy storage mechanism of its Zn2+/H+ co-storage is investigated and elucidated. Additionally, this work provides new insights and perspectives for the investigation and application of amorphous cathodes for aqueous zinc ion batteries.
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Following myocardial ischemic injury, the most effective clinical intervention is timely restoration of blood perfusion to ischemic but viable myocardium to reduce irreversible myocardial necrosis, limit infarct size, and prevent cardiac insufficiency. However, reperfusion itself may exacerbate cell death and myocardial injury, a process commonly referred to as ischemia/reperfusion (I/R) injury, which primarily involves cardiomyocytes and cardiac microvascular endothelial cells (CMECs) and is characterized by myocardial stunning, microvascular damage (MVD), reperfusion arrhythmia, and lethal reperfusion injury. MVD caused by I/R has been a neglected problem compared to myocardial injury. Clinically, the incidence of microvascular angina and/or no-reflow due to ineffective coronary perfusion accounts for 5-50% in patients after acute revascularization. MVD limiting drug diffusion into injured myocardium, is strongly associated with the development of heart failure. CMECs account for > 60% of the cardiac cellular components, and their role in myocardial I/R injury cannot be ignored. There are many studies on microvascular obstruction, but few studies on microvascular leakage, which may be mainly due to the lack of corresponding detection methods. In this review, we summarize the clinical manifestations, related mechanisms of MVD during myocardial I/R, laboratory and clinical examination means, as well as the research progress on potential therapies for MVD in recent years. Better understanding the characteristics and risk factors of MVD in patients after hemodynamic reconstruction is of great significance for managing MVD, preventing heart failure and improving patient prognosis.
Subject(s)
Heart Failure , Myocardial Infarction , Myocardial Reperfusion Injury , Humans , Endothelial Cells/metabolism , Myocardial Infarction/metabolism , Myocardium/metabolism , Myocardial Reperfusion Injury/metabolism , Heart Failure/metabolismABSTRACT
A novel type of three-dimensional network structure, covalent organic frameworks (COFs) aerogel, was fabricated and applied to dispersive solid-phase extraction (dSPE) of quinolone antibiotics (QAs). Density functional theory (DFT) was applied to investigate the possible interaction mechanism and results confirmed that the strong adsorption affinity is attributed to the intralayer hydrogen bonds and π-π interaction. Furthermore, a sensitive analytical method based on COFs-aerogel for determining quinolone antibiotics residues in water and honey samples was developed and HPLC-MS/MS was used for sample detection and quantification. Under the optimal conditions, COFs-aerogel exhibited a wide linearity (0.1-500 ngâL-1), low limits of detection (0.02-0.06 ngâL-1), and good precision (RSD Ë 10%) for selected QAs. A preliminary practical application of the developed method was proved by the efficient detection of quinolone antibiotics in water and food samples with good recoveries (68.2-104% and 64.0-100% for water and honey samples, respectively). Combining the experimental data with theoretical calculation, results illustrated that COFs-aerogel holds a great potential to capture contaminants and address environmental and food safety issues.
Subject(s)
Metal-Organic Frameworks , Quinolones , Tandem Mass Spectrometry , Anti-Bacterial Agents , Solid Phase Extraction , WaterABSTRACT
Objectives: Excessive inflammatory responses and reactive oxygen species (ROS) formation play pivotal roles in the pathogenesis of sepsis. Penfluroidol (PF), an oral long-acting antipsychotic drug, has been suggested to possess diverse biological properties, including antischizophrenia, antitumour effect, and anti-inflammatory activity. The purpose of this research was to explore the anti-inflammatory and antioxidative effects of penfluroidol on lipopolysaccharide (LPS)-related macrophages. Methods: The viability of RAW264.7 and THP-1 cells was measured by Enhanced Cell Counting Kit-8 (CCK-8). The production of nitric oxide was evaluated by the Nitric Oxide Assay Kit. The generation of pro-inflammatory monocytes was detected by qRT-PCR (quantitative real-time PCR) and ELISA (enzyme-linked immunosorbent assay). Oxidative stress was assessed by measuring ROS, malondialdehyde (MDA), and superoxide dismutase (SOD) activity. The protein expression of the Nrf2/HO-1/NLRP3 inflammasome was detected by western blotting. Results: Our results indicated that no cytotoxic effect was observed when RAW264.7 and THP-1 cells were exposed to PF (0-1 µm) and/or LPS (1 µg/ml) for 24 hr. The data showed that LPS, which was repressed by PF, facilitated the generation of the pro-inflammatory molecules TNF-α and IL-6. In addition, LPS contributed to increased production of intracellular ROS compared with the control group, whereas the administration of PF effectively reduced LPS-related levels of ROS. Moreover, LPS induced the generation of MDA and suppressed the activities of SOD. However, PF treatment strongly decreased LPS-induced MDA levels and increased SOD activities in the RAW264.7 and THP-1 cells. Furthermore, our research confirmed that penfluroidol repressed the secretion of pro-inflammatory molecules by limiting the activation of the NLRP3 inflammasome and reducing oxidative effects via the Nrf2/HO-1 signaling pathway. Conclusion: Penfluroidol attenuated the imbalance of the inflammatory response by suppressing the activation of the NLRP3 inflammasome and reduced oxidative stress via the Nrf2/HO-1 signaling pathway in LPS-induced macrophages.
Subject(s)
3,4-Methylenedioxyamphetamine , Lipopolysaccharides , Inflammasomes , Macrophages , NF-E2-Related Factor 2 , Nitric Oxide , NLR Family, Pyrin Domain-Containing 3 Protein , Oxidative Stress , Reactive Oxygen Species , Signal Transduction , Superoxide Dismutase , THP-1 Cells , RAW 264.7 Cells , Humans , Animals , MiceABSTRACT
The functional food ingredients of apple juice can significantly change during processing, transportation, and storage, thus affecting the quality of the product. A simple and derivation-free analytical method based on ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was developed and optimized for the simultaneous determination of functional food ingredients in apple juice bought in the market. Cleanup steps and chromatographic conditions were optimized to remove interference and decrease the matrix effect. The nine target analytes were separated on an Acquity UPLC system equipped with a BEH C18 column and detected by electrospray ionization source (ESI) operating in positive subsection acquisition mode under multiple reaction monitoring (MRM) conditions. The results showed that p-hydroxybenzoic acid, protocatechuate, caffeic acid, chlorogenic acid, epicatechin, phloridzin, hyperoside, procyanidin B2, and rutin could be sufficiently separated for content determination within 6 min. In the concentration range of 20 µg/L-50 mg/L, nine standard samples exhibited a good linear fit with correlation coefficients above .985.
ABSTRACT
The design of an efficient OER catalyst is significant for water splitting. Metal-organic frameworks (MOFs) are emerging as promising electrocatalysts due to their diversity of structure and tunability of function. In this paper, 2D FexCo1-x-MOF1/NF with an extended ligand (biphenyl-4,4'-dicarboxylic acid, BPDC) is constructed on nickel foam by a solvothermal method. Compared with the MOF2 synthesized by using BDC (1,4-bezenedicarboxylate), MOF1 shows excellent performance. Among MOF1, Fe0.5Co0.5-MOF1/NF exhibits outstanding performance with a low overpotential (217 mV) and a small Tafel slope (31.16 mV Dec-1) at 10 mA cm-2 and performs well at a high current density. In addition, the catalyst is remarkable in terms of durability both in alkaline solution and simulated seawater. The synergetic effect between Fe and Co and more active sites exposed play an important role in improving the OER activity. This work provides an effective strategy for the rational design of MOFs as inexpensive electrocatalysts.
ABSTRACT
Solar-driven water splitting offers a leading-edge approach to storing abundant and intermittent solar energy and producing hydrogen as a clean and sustainable energy carrier. More importantly, constructing well-designed photocatalysts is a promising approach to develop clean hydrogen energy. In this paper, flower spherical UiO-66-(SCH3)2/ZnIn2S4 (UiOSC/ZIS) photocatalysts are successfully synthesized by a simple two-step hydrothermal method, and they exhibit high hydrogen production activity in light-driven water splitting. The optimized 30-UiOSC/ZIS (the content of UiOSC was 30 mg) composite exhibits optimal hydrogen production activity with a hydrogen production of 3433 µmol g-1 h-1, which is 5 and 235 times higher than that of pure ZIS and UiOSC, respectively. In addition, a long-cycling stability test has shown that the UiOSC/ZIS composite has good stability and recyclability. Experimental and characterization results show the formation of a type-II heterojunction between UiOSC and ZIS. This effectively suppresses the recombination of electrons-holes and promotes the carrier transfer, thus significantly improving the hydrogen production performance. This research further promotes the application of UiO-66-(SCH3)2 in the field of photocatalytic hydrogen production and provides a reference for the rational design of UiO-66-based composite photocatalysts.
ABSTRACT
Seeking new methods to modulate the structure of metal-organic frameworks (MOFs) for diverse applications, particularly for water splitting, is intensively urgent but challenging. Herein, a simple hydrothermal method employing HCl as the modulator is developed to synthesize a series of NiFe-MOF-n/NF. The amount of HCl modulator not only changes the elemental composition and crystal structure but also modulates the electronic structure of NiFe-MOF-n/NF, thus improving intrinsic activity. Owing to the synergetic interactions between Ni and Fe atoms, free-standing feature, the optimized NiFe-MOF-2/NF yields excellent OER activity with overpotentials of 209 and 260 mV at 10 and 100 mA cm-2, respectively, a small Tafel slope of 36.4 mV dec-1 and excellent OER stability for 24 h at 100 mA cm-2 in 1 M KOH. This demonstrates that NiFe-MOF-2/NF are in situ converted into metal oxide/oxyhydroxide after OER, thereby serving as the real active sites. This study offers a feasible way to fabricate low-cost, efficient MOF-based electrocatalysts.
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The present study aimed to explore the improvement of the bioactivity of ginger peel polysaccharides (GPs) by the modification of zinc after structural characterization. The obtained GP-Zn (II) complexes consisted dominantly of glucose and galactose in a mass proportion of 95.10:2.10, with a molecular weight of 4.90 × 105 Da and a Zn content of 21.17 mg/g. The chelation of GPs and Zn (II) was mainly involved in the O-H of hydroxyl groups, and this interaction reduced the crystallinity and decreased the asymmetry of GPs, with a slight effect on the thermal stability. The administration of GPs and their Zn (II) complexes effectively alleviated CuSO4-induced inflammatory response in zebrafish (Tg: zlyz-EGFP) via down-regulating the mRNA expression levels of pro-inflammatory cytokines (IL-1ß, IL-6, IL-8, IL-12 and TNF-α) and upregulating the expression of anti-inflammatory cytokine (IL-10). Furthermore, the modification of Zn (II) enhanced the inflammation-inhibiting effect of polysaccharides. Therefore, GP-Zn (II) complexes could be applied as a candidate anti-inflammatory agent for the treatment of chronic inflammation-related diseases.
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The UiO-66 family shows promising photocatalytic prospects in water splitting for hydrogen evolution under visible light irradiation due to its suitable band gap and adequate active sites. In this work, novel Ni2P/UiO-66-(SCH3)2 composites were prepared by a simple solvothermal method. These as-synthesized samples were fully characterized by XRD, SEM, TEM, HRTEM, EDS, and XPS methods. The effectiveness of visible light driven photocatalytic water-splitting to produce hydrogen was investigated in the presence of sacrificial agents. The results showed that the optimal hydrogen yield of 5 wt% Ni2P/UiO-66-(SCH3)2 is 3724.22 µmol g-1 h-1, reaching almost 187 times that of pristine UiO-66-(SCH3)2 (19.93 µmol g-1 h-1). Meanwhile, long term cycling stability tests also showed that Ni2P/UiO-66-(SCH3)2 composites present an excellent photocatalytic H2 production stability. Photoelectrochemical performance analysis revealed that the high catalytic activity of the composite materials could be associated with the synergistic effect of UiO-66-(SCH3)2 and Ni2P. Light stimulates UiO-66-(SCH3)2 to generate electrons and holes, and Ni2P as a cocatalyst could effectively transmit electrons and boost photogenerated charge separation. This work provides a reference for exploring UiO-66 family catalysts with good catalytic activity.
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The identification of pork meat quality is a significant issue in food safety. In this paper, a novel strategy was proposed for identifying pork meat samples at different storage times via Fourier transform near-infrared (FT-NIR) spectroscopy and fuzzy clustering algorithms. Firstly, the FT-NIR spectra of pork meat samples were collected by an Antaris II spectrometer. Secondly, after spectra preprocessing with multiplicative scatter correction (MSC), the orthogonal linear discriminant analysis (OLDA) method was applied to reduce the dimensionality of the FT-NIR spectra to obtain the discriminant information. Finally, fuzzy C-means (FCM) clustering, K-harmonic means (KHM) clustering, and Gustafson-Kessel (GK) clustering were performed to establish the recognition model and classify the feature information. The highest clustering accuracies of FCM and KHM were both 93.18%, and GK achieved a clustering accuracy of 65.90%. KHM performed the best in the FT-NIR data of pork meat considering the clustering accuracy and computation. The overall experiment results demonstrated that the combination of FT-NIR spectroscopy and fuzzy clustering algorithms is an effective method for distinguishing pork meat storage times and has great application potential in quality evaluation of other kinds of meat.
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Verticillium wilt is a highly destructive fungal disease that attacks a broad range of plants, including many major crops. However, the mechanism underlying plant immunity toward Verticillium dahliae is very complex and requires further study. By combining bioinformatics analysis and experimental validation, we investigated plant defence responses against V. dahliae infection in the model plant Arabidopsis thaliana L. A total of 301 increased and 214 decreased differentially abundant proteins (DAPs) between mock and infected wild type (WT) plants were acquired and bioinformatics analyses were then conducted and compared (increased vs decreased) in detail. In addition to the currently known mechanisms, several new clues about plant immunity against V. dahliae infection were found in this study: (1) exosome formation was dramatically induced by V. dahliae attack; (2) tryptophan-derived camalexin and cyanogenic biosynthesis were durably promoted in response to infection; and (3) various newly identified components were activated for hub immunity responses. These new clues provide valuable information that extends the current knowledge about the molecular basis of plant immunity against V. dahliae infection.
Subject(s)
Arabidopsis , Arabidopsis/genetics , Plant Diseases , Plant Proteins/metabolism , Proteomics , Tryptophan , VerticilliumABSTRACT
The thermocapillary flow instabilities of silicon melt in a cylindrical pool with a rotating disk on the free surface (a simplified model of the Czochralski crystal growth) are numerically investigated by using the linear stability analysis. The complete neutral or critical stability curves are determined. Results show that the neutral stability curves form a closed region in the parameter plane, in which the steady axisymmetric flow is linearly stable. Two types of rotating wave (RW1 and RW2) instabilities and two types of hydrothermal wave (HTW1 and HTW2) instabilities are found. The energy analysis shows that all the instabilities are hydrodynamic (inertial) in nature. Specifically, RW1 and RW2 are caused by the azimuthal shear induced by the crystal rotation, while HTW1 and HTW2 are caused by the radial shear induced by the thermocapillary force.
ABSTRACT
Functional groups modified metal-organic frameworks (MOFs) was synthesized via a pre-tailor method and served as an adsorbent for perfluorooctanoic acid (PFOA) removal. The material was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction and N2 sorption-desorption. Monte Carlo simulation and molecular dynamics are derived to predict the possible molecular packing and adsorption mechanism. The Hirshfeld surface with reduced density gradient analysis demonstrates that PFOA is adsorbed on MOF-X mainly affected by van der Waals interactions and steric effects. Adsorption kinetics and isotherms were investigated on the basis of a static experiment. The pseudo-second-order kinetic model and Langmuir isotherm were fitted well to characterize adsorption process. Hereinto, amino-modified MOFs reached the highest adsorption efficiency and the maximum capacity was 185.6 mg/g. Combing the experimental data with theoretical simulation, results indicated that functional group modification is an effective approach to alter the crystal structure and then affect the adsorptive properties of MOFs.
Subject(s)
Fluorocarbons , Metal-Organic Frameworks , Water Pollutants, Chemical , Adsorption , Caprylates , Kinetics , Spectroscopy, Fourier Transform Infrared , Water Pollutants, Chemical/analysisABSTRACT
Autism spectrum disorders (ASD), also known as childhood autism, is a common neurological developmental disorder. Although it is generally believed that genetic factors are a primary cause for ASD development, more and more studies show that an increasing number of ASD diagnoses are related to environmental exposure. Epidemiological studies indicated that perinatal exposure to endocrine disruptors might cause neurodevelopmental disorders in children. Di-(2-ethylhexyl) phthalate (DEHP) is widely used as a plasticizer in many products. To explore the neurodevelopmental effect induced by perinatal exposure to DEHP on rat offspring, and the potential mechanisms, female Wistar rats were exposed to 1, 10, and 100 mg/kg/day DEHP during pregnancy and lactation, while valproic acid (VPA) was used as a positive control. The behavior tests showed that rat pups exposed to VPA and 100 mg/kg/day DEHP were not good as those from the control group in both their socialability and social novelty. Expression of mTOR pathway-related components increased while the number of autophagosomes decreased in the brain tissue of the rat offspring exposed to 100 mg/kg/day DEHP. In addition, perinatal exposure to DEHP at all dosages decreased the level of autophagy proteins LC3II and Beclin1 in the brain tissue of rat pups. Our results indicated that perinatal DEHP exposure would induce ASD-like behavioral changes in rat offspring, which might be mediated by activation of the mTOR signaling pathway, and inhibition of autophagy in the brain.