Mesoporous amorphous non-noble metals as versatile substrates for high loading and uniform dispersion of Pt-group single atoms.

Atomically dispersed Pt-group metals are promising as nanocatalysts because of their unique geometric structures and ultrahigh atomic utilization. However, loading isolated Pt-group metals in single-atom alloys (SAAs) with distinctive bimetallic sites is challenging. In this study, we present amorphous mesoporous Ni boride (Ni-B) as an ideal substrate to uniformly disperse Pt atoms with tunable loadings (1.7 to 12.2 wt %). The effect of the morphology, composition, and crystal phase of the Ni-B host on the growth and dispersion of Pt atoms is discussed. The resulting amorphous Pt-Ni-B mesoporous nanospheres exhibit superior electrocatalytic H2 evolution performance in acidic media. This strategy holds the potential to synthesize a diverse library of mesoporous amorphous Pt-group SAAs, by leveraging functional amorphous nanostructured 3d transition-metal borides as substrates, thereby proposing a comprehensive strategy to control atomically dispersed Pt-group metals.

SeMet alleviates AFB1-induced oxidative stress and apoptosis in rabbit kidney by regulating Nrf2//Keap1/NQO1 and PI3K/AKT signaling pathways.

The purpose of this study was to explore the protective effect of SeMet on renal injury induced by AFB1 in rabbits and its molecular mechanism. Forty rabbits of 35 days old were randomly divided into control group, AFB1 group (0.3 mg AFB1/kg b.w), 0.2 mg/kg Se + AFB1 group (0.3 mg AFB1/kg b.w + 0.2 mg SeMet/kg feed) and 0.4 mg/kg Se + AFB1 group (0.3 mg AFB1/kg b.w + 0.4 mg SeMet/kg feed). The SeMet treatment group was fed different doses of SeMet diets every day for 21 days. On the 17-21 day, the AFB1 treatment group, the 0.2 mg/kg Se + AFB1 group and the 0.4 mg/kg Se + AFB1 group were administered 0.3 mg AFB1 /kg b.w by gavage (dissolved in 0.5 ml olive oil) respectively. The results showed that AFB1 poisoning resulted in the changes of renal structure, the increase of renal coefficient and serum biochemical indexes, the ascent of ROS and MDA levels, the descent of antioxidant enzyme activity, and the significant down-regulation of Nrf2, HO-1 and NQO1. Besides, AFB1 poisoning increased the number of renal apoptotic cells, rised the levels of PTEN, Bax, Caspase-3 and Caspase-9, and decreased the levels of PI3K, AKT, p-AKT and Bcl-2. In summary, SeMet was added to alleviate the oxidative stress injury and apoptosis of kidney induced by AFB1, and the effect of 0.2 mg/kg Se + AFB1 is better than 0.4 mg/kg Se + AFB1.

Surface Hydrogen Bond-Induced Oxygen Vacancies of TiO2 for Two-Electron Molecular Oxygen Activation and Efficient NO Oxidation.

Defect engineering can provide a feasible approach to achieving ambient molecular oxygen activation. However, conventional surface defects (e.g., oxygen vacancies, OVs), featured with the coordinatively unsaturated metal sites, often favor the reduction of O2 to •O2- rather than O22- via two-electron transfer, hindering the efficient pollutant removal with high electron utilization. Herein, we demonstrate that this bottleneck can be well discharged by modulating the electronic structure of OVs via phosphorization. As a proof of concept, TiO2 nanoparticles are adopted as a model material for NaH2PO2 (HP) modification, in which HP induces the formation of OVs via weakening the Ti-O bonds through the hydrogen bond interactions. Additionally, the formed Ti-O-P covalent bond refines the electronic structure of OVs, which enables rapid electron transfer for two-electron molecular oxygen activation. As exemplified by NO oxidation, HP-modified TiO2 with abundant OVs achieved complete NO removal with high selectivity for benign nitrate, superior to that of pristine TiO2. This study highlights a promising approach to regulate the O2 activation via an electronic structure modulation and provides fresh insights into the rational design of a photocatalyst for environmental remediation.

Microwave assisted synthesis of PQ-GDY@NH2-UIO-66(Zr) for improved photocatalytic removal of NOx under visible light.

Pyrazinoquinoxaline-based graphdiyne (PQ-GDY) contains a fixed number of sp-sp2 hybridized carbon atoms and pyrazine-like sp2 hybridized N atoms. In this paper, NH2-UIO-66(Zr) on PQ-GDY substrate was successfully constructed with the help of microwave-assisted heating. PQ-GDY surface acts as a microwave antenna under microwave irradiation to rapidly absorb microwave energy and form hot spots (hot spot effect), which facilitates the formation of well-dispersed NH2-UIO-66(Zr) with good crystallinity. Transient absorption spectra show that high hole transport property of PQ-GDY can accelerate the migration of photogenerated holes from NH2-UIO-66(Zr) to PQ-GDY and greatly reduce the recombination rate of photogenerated electrons and holes due to the strong interaction between PQ-GDY and NH2-UIO-66(Zr). Under visible light (λ ≥ 420 nm), PQ-GDY@NH2-UIO-66(Zr) shows high photocatalytic stability and high NOx removal rate up to 74%, which is 44% higher than that of primitive NH2-UIO-66(Zr). At the same time, it inhibits the formation of toxic by-products (NO2) and limits its concentration to a low level.

Modulating the Active Hydrogen Adsorption on Fe─N Interface for Boosted Electrocatalytic Nitrate Reduction with Ultra-Long Stability.

The electrocatalytic reduction of nitrate (NO3 - ) to nitrogen (N2 ) is an environmentally friendly approach for efficient N-cycle management (toward a nitrogen-neutral cycle). However, poor catalyst durability and the competitive hydrogen evolution reaction significantly impede its practical application. Interface-chemistry engineering, utilizing the close relationship between the catalyst surface/interface microenvironment and electron/proton transfer process, has facilitated the development of catalysts with high intrinsic activity and physicochemical durability. This study reports the synthesis of a nitrogen-doped carbon-coated rice-like iron nitride (RL-Fe2 N@NC) electrocatalyst with excellent electrocatalytic nitrate-reduction reaction activity (high N2 selectivity (≈96%) and NO3 - conversion (≈86%)). According to detailed mechanistic investigations by in situ tests and theoretical calculations, the strong hydrogenation ability of iron nitride and enhanced nitrate enrichment of the system synergistically contribute to the rapid hydrogenation of nitrogen-containing species, increasing the intrinsic activity of the catalyst and reducing the occurrence of the competing hydrogen-evolution side reaction. Moreover, RL-Fe2 N@NC shows excellent stability, retaining good NO3 - -to-N2 electrocatalysis activity for more than 40 cycles (one cycle per day). This paper could guide the interfacial design of Fe-based composite nanostructures for electrocatalytic nitrate reduction, facilitating a shift toward nitrogen neutrality.

Hydroxyl Radical-Mediated Efficient Photoelectrocatalytic NO Oxidation with Simultaneous Nitrate Storage Using A Flow Photoanode Reactor.

The selective conversion of dilute NO pollutant into low-toxic product and simultaneous storage of metabolic nitrogen for crop plants remains a great challenge from the perspective of waste management and sustainable chemistry. This study demonstrates that this bottleneck can be well tackled by refining the reactive oxygen species (ROS) on Ni-modified NH2 -UiO-66(Zr) (Ni@NU) using nickel foam (NF) as a three-dimensional (3D) substrate through a flow photoanode reactor via the gas-phase photoelectrocatalysis. By rationally refining the ROS to ⋅OH, Ni@NU/NF can rapidly eliminate 82 % of NO without releasing remarkable NO2 under a low bias voltage (0.3 V) and visible light irradiation. The abundant mesoporous pores on Ni@NU/NF are conducive to the diffusion and storage of the formed nitrate, which enables the progressive conversion NO into nitrate with selectivity over 99 % for long-term use. Through calculation, 90 % of NO could be recovered as the nitrate species, indicating that this state-of-the-art strategy can capture, enrich and recycle the pollutant N source from the atmosphere. This study offers a new perspective of NO pollutant treatment and sustainable nitrogen exploitation, which may possess great potential to the development of highly efficient air purification systems for industrial and indoor NOx control.

Tailoring the Asymmetric Structure of NH2 -UiO-66 Metal-Organic Frameworks for Light-promoted Selective and Efficient Gold Extraction and Separation.

Designing adsorption materials with high adsorption capacities and selectivities is highly desirable for precious metal recovery. Desorption performance is also particularly crucial for subsequent precious metal recovery and adsorbent regeneration. Herein, a metal-organic framework (MOF) material (NH2 -UiO-66) with an asymmetric electronic structure of the central zirconium oxygen cluster has an exceptional gold extraction capacity of 2.04 g g-1 under light irradiation. The selectivity of NH2 -UiO-66 for gold ions is up to 98.8 % in the presence of interfering ions. Interestingly, the gold ions adsorbed on the surface of NH2 -UiO-66 spontaneously reduce in situ, undergo nucleation and growth and finally achieve the phase separation of high-purity gold particles from NH2 -UiO-66. The desorption and separation efficiency of gold particles from the adsorbent surface reaches 89 %. Theoretical calculations indicate that -NH2 functions as a dual donor of electrons and protons, and the asymmetric structure of NH2 -UiO-66 leads to energetically advantageous multinuclear gold capture and desorption. This adsorption material can greatly facilitate the recovery of gold from wastewater and can easily realize the recycling of the adsorbent.

An unprecedented ergostane with a 6/6/5 tricyclic 13(14 → 8)abeo-8,14-seco skeleton from Talaromyces adpressus.

Talasterone A (1), an unprecedented 6/6/5 tricyclic 13(14 â†’ 8)abeo-8,14-seco-ergostane steroid, together with two known congeners dankasterone B (2) and (14ß,22E)-9,14-dihydroxyergosta-4,7,22-triene-3,6-dione (3), were characterized from Talaromyces adpressus. The structure of 1 with absolute configuration was elucidated based on NMR spectroscopic data and ECD calculation. Compound 2 belongs to a class of unconventional 13(14 â†’ 8)abeo-ergostanes, which have been renewed via the 1,2-migration of C-13-C-14 bond to C-8. In addition, compound 1 represents the first example of ergostane with a tricyclic 13(14 â†’ 8)abeo-8,14-seco-ergostane skeleton. The proposed biosynthetic pathway was established with the support of the coisolation of the known congeners from the producing organism. It is especially noteworthy that compound 1 exhibited potent anti-inflammatory activity with an IC50 value of 8.73 ± 0.66 µM, inhibiting the NF-κB pathway and thus reducing the production of proinflammatory cytokines.

Diamond in the rough: Polishing waste polyethylene terephthalate into activated carbon for CO2 capture.

The scientific community has believed the potential of waste PET plastics as an effective carbon precursor, however, developing PET-derived activated carbons (PETACs) for a specific application is still a challenge we are facing. To overcome the limitation, a whole chain from development method screening to experiments design, finally to sample optimization, for a sample with promising performance, is proposed in this work. By employing PETACs as CO2 adsorbents, the waste PET plastics, which we believed the "diamond in the rough", have been polished successfully. Therewith the problems of plastic pollution and the greenhouse effect could be simultaneously solved. The first half part of this paper is a mini review: the PETACs development methods were reviewed and the most suitable solution to develop CO2 adsorbent, i.e., the two-step chemical activation method, was selected. In addition to that, the necessary procedure variables and their value range were determined. In the second half part, the central composite design method was applied for experiments design in which the procedure variables obtained were regarded as the independent indicators (factors here) while the performance indicators, including yield, CO2 adsorption uptake, and CO2 over N2 selectivity, were treated as the dependent indicators (responses here). The responses were obtained through the characterization of the samples developed and statistical analysis could be applied to reveal the relations between the factors and responses. A high-value PETAC, P600K600-1.5, with the highest gas selectivity (22.189) and decent CO2 adsorption uptake (3.933 mmol/g) was successfully designed.

Dual-emitting metal-organic frameworks for ratiometric fluorescence detection of fluoride and Al3+ in sequence.

Fluoride (F-) and Al3+ are two common ions existing in drinking water and natural water bodies. Excessive intake of F- can lead to serious health issues such as fluorosis and bone diseases while accumulated consumption of Al3+ may cause neurotoxicity-based diseases. Developing a fast, reliable, and sensitive sensor for visually detecting both F- and Al3+ is of great significance. In the present work, a ratiometric fluorescence sensor was constructed by incorporating rhodamine B (RhB) in situ into a zirconium-based metal-organic framework, UiO-66-NH2. The obtained nanocomposite UiO-66-NH2@RhB exhibited similar octahedral structure to UiO-66-NH2 with high BET surface area, and showed two emission peaks at 450 nm and 585 nm. The blue fluorescence from UiO-66-NH2 was enhanced by the addition of F- while subsequent Al3+ addition diminished the increased fluorescence intensity, and the red emission from RhB as the reference remained unchangeable to improve the detection precision. Under optimal conditions, detection of limits as low as 1.55 µM for F- and 0.54 µM for Al3+ in aqueous solution were achieved with good selectivity. High recoveries in drinking water samples were also acquired, showing potential applications of this ratiometric fluorescence sensor for practical evaluation of F- and Al3+.

A population-based genomic epidemiological study of the source of tuberculosis infections in an emerging city: Shenzhen, China.

BACKGROUND: Tuberculosis (TB) in emerging cities is often a disease of recent immigrants, and understanding this epidemiology is crucial for designing effective control and prevention strategies. METHODS: We conducted a retrospective population-based genomic epidemiological study of culture-positive pulmonary TB patients diagnosed between June 2014 and November 2017 in the Bao'an District of Shenzhen, a Chinese city with dramatic recent growth. After whole genome sequencing, transmission clusters were defined as strains differing by no more than 12 SNPs. FINDINGS: Of 1696 culture-positive TB patients, 93•8% (1591/1696) were migrants, with 51•6% (821/1591) employed in housekeeping or unemployed. Of the 1460 migrants with known residence time, 47•7% (697/1460) developed TB within two years after arriving in Bao'an. Only 12•2% (207/1696) of Bao'an isolates were in genomic clusters, indicating that recent transmission was not the primary cause of TB in Bao'an. The isolates' median terminal branch length was 56 SNPs, more than could have accumulated since the arrival of the migrants in Bao'an. The migrants' isolates had genotypic distributions similar to those in their home provinces. One strain isolated in Bao'an belonged to a clade circulating in the patient's home province, providing further evidence that the strains were brought to Bao'an with the migrants. INTERPRETATION: TB in the Bao'an District is principally caused by reactivation of infections acquired by migrants in their home provinces. Nearly half developed TB within two years after arriving in Bao'an, suggesting a need for increased TB screening of migrants, especially housekeeping workers and the unemployed. FUNDING: Sanming Project of Medicine in Shenzhen; National Science and Technology Major Project of China; Natural Science Foundation of China.

Valorization of waste polyethylene terephthalate plastic into N-doped microporous carbon for CO2 capture through a one-pot synthesis.

Valorization of waste polyethylene terephthalate (PET) plastic into microporous carbon with N-doping treatment was successfully performed in a one-pot synthesis and the N-doped microporous carbon was used for CO2 capture, which can mitigate plastic pollution and climate change simultaneously. The PET-derived microporous carbon developed by KOH activation and urea treatment in a one-pot synthesis at 700 °C exhibited the highest CO2 adsorption uptake of 6.23 mmol g-1 at 0 °C and 4.58 mmol g-1 at 25 °C (1 atm). The Langmuir and pseudo second-order models displayed well-fitting relationships with equilibrium and kinetic experimental data obtained in this study. The N-doped microporous carbon showed high CO2 selectivity over N2, implying that it is feasible for treating flue gases (10% CO2 and 90% N2) at 50 °C. In addition, the CO2 uptake was not only affected by micropores but also related with nitrogen and oxygen functional groups. Compared to the porous carbon prepared by two-pot synthesis where KOH activation and urea treatment were conducted separately, the porous carbon prepared by one-pot synthesis had higher oxygen contents and higher CO2 adsorption uptake. All of findings implied that the N-doped microporous carbon was successfully developed from waste PET plastic for capturing CO2 and can play a promising role in both sustainable waste management and environmental protection.

Betulin isolated from Pyrola incarnata Fisch. inhibited lipopolysaccharide (LPS)-induced neuroinflammation with the guidance of computer-aided drug design.

This study aims to investigate active phytochemicals isolated from Pyrola incarnata Fisch. (P. incarnata) and their protection against neuroinflammation induced by LPS. Betulin, accompanied with other 9 compounds, were isolated from P. incarnata and elucidated by spectroscopic analysis (1H-, 13C NMR). ELISA kits and the measurement of NO production based on Griess reaction showed that betulin (5) (250 µg/mL) could suppress LPS-induced activation of microglial cell BV-2 better than others by inhibiting inflammatory cytokines (TNF-α, IL-6, IL-1ß) expression and NO production. With the guidance of computer-aided drug design and the analysis of biological experiment, we demonstrated betulin could reduce LPS-induced iNOS expression, prevent JNKs pathways, and down-regulate the phosphorylation levels of NF-κB/p65. In conclusion, betulin isolated from P. incarnata possessed outstanding anti-neuroinflammation potential, presumably related to iNOS expression, JNKs and NF-κB/p65 pathways. Therefore, Pyrola incarnata may be a valuable natural resource and betulin is a potential drug for the treatment of neurodegenerative disorders by inhibiting inflammatory mediators.

A Comprehensive Review of the Genus Pyrola Herbs in Traditional Uses, Phytochemistry and Pharmacological Activities.

Pyrola (Pyrolaceae), also known as Luxiancao/in China, was recorded in Sheng Nong's Herbal Classic listed in top grade. Pyrola herbs were used as medicinal plants for a long history with wide-ranging activities such as nourishing kidney-yang, strengthening muscles and bones, activating blood, stopping bleeding, dispelling rheumatism, and eliminating dampness. Currently, the research on Pyrola plants is increasing year by year but there is no comprehensive and detailed review concerning genus Pyrola. This review aims to sum up the updated and comprehensive information about botany and traditional use, phytochemistry, pharmacological activities and safety by analyzing the information available on Pyrola plants via internationally accepted scientific databases. Collectively, more than 100 compounds have been isolated from the Pyrola plants. Furthermore, a total of 33 prescriptions containing Pyrola plants are compiled in this review. Pyrola plants are used as indispensable agents in traditional Chinese medicine due to its activities of antimicrobial, anti-inflammatory, antioxidant, lipidlowering, cardiovascular and cerebrovascular protection, proliferation of osteoblasts promoting, antineoplastic and etc. Further work should be developed on the elucidation of structure-function relationship, understanding of multi-target pharmacological effects, as well as developing its application both in clinical usage and functional food for research and development of Pyrola plants.

Pyrola incarnata demonstrates neuroprotective effects against ß-amyloid-induced memory impairment in mice.

This study aims to investigate the neuroprotective effects of Pyrola incarnata against ß-amyloid-induced memory impairment in mice. Ethanol extract of Pyrola incarnata (EPI) was obtained and led to eleven phytochemicals successfully by isolation and purification, which were elucidated by spectroscopic analysis (1H NMR, 13C NMR and HR-ESI-MS). Thereinto, ursolic acid was gained as most abundant monomer. C57BL/6 mice were intracerebroventricular injected with aggregated Aß25-35. Open-field test, Barnes maze test and Morris water maze were conducted for evaluating cognition processes of EPI and ursolic acid. EPI significantly improved learning and memory deficits, attenuated the Aß25-35 level of deposition immunohistochemically. Further studies revealed that ursolic acid as bioactive phytochemical of P. incarnata improved spatial memory performance and ameliorated Aß25-35 accumulation by activating microglia cells and up-regulating Iba1 level in the hippocampus. These findings suggest P. incarnata could improve the cognition of mice and be a promising natural source for the treatment of neurodegenerative disease.

Structurally Diverse Meroterpenoids from a Marine-Derived Aspergillus sp. Fungus.

Three new meroterpenoids, asperaustins A-C (1-3), and seven known analogues (4-10) were isolated from a marine-derived Aspergillus sp. fungus. The structures and absolute configurations of these new compounds were unequivocally determined by extensive spectroscopic analyses and single-crystal X-ray diffraction analyses. Asperaustin A (1) possesses an unusual spiro[4.5]deca-3,6-dien-2-one moiety with a unique 5/6/6/6/5 pentacyclic skeleton. The absolute configurations of austinoneol A (7) and precalidodehydroaustin (9) were determined by single-crystal X-ray diffraction analyses using Cu Kα radiation for the first time.

Energy dissipation evaluation of temperature swing adsorption (TSA) cycle based on thermodynamic entropy insights.

The special report of the Intergovernmental Panel on Climate Change's (IPCC) on global warming of 1.5 °C marks a critical point in climate negotiations, which emphasizes the importance to control the CO2 level in the atmosphere. The current technology cluster of CO2 capture is still energy-intensive which results in a substantial increase in costs, thus the efficient conversion among various forms of energy is the major topic of research. Considering that most of the existing research are primarily based on the viewpoint of energy conservation on a specific case study, the results thus could not be efficiently generalized as a condensed mechanism of energy dissipation. In this work, the entropy generation evaluation of a 4-step temperature swing adsorption (TSA) process was presented as a sample. The values and contribution distributions of various entropy generation in the thermodynamic cycle were calculated to evaluate the major energy dissipation. The results on contribution distribution of entropy generation and heat required were compared, the entropy generation distribution contributed by heat transfer decreases from 63.27% to 53.72% with internal heat recovery (IHR) method integrated. Thus the entropy generation saving potential of IHR method could be proved.

An Efficient, One-Pot Transamidation of 8-Aminoquinoline Amides Activated by Tertiary-Butyloxycarbonyl.

The efficient, one-pot access to the transamidation of 8-aminoquinoline (8-AQ), notorious for its harsh removal conditions, has been widely employed as an auxiliary in C⁻H functionalization reactions due to its strong directing ability. In this study, the facile and mild Boc protection of the corresponding 8-AQ amide was critical to activate the amide C(acyl)⁻N bond by twisting its geometry to lower the amidic resonance energy. Both aryl and alkyl amines proceeded transamidation in one-pot, user-friendly conditions with excellent yields.

Entropy Analysis of Temperature Swing Adsorption for CO2 Capture Using the Computational Fluid Dynamics (CFD) Method.

Carbon capture by adsorption is supposed to be an effective method to reduce CO2 emissions, among which Temperature Swing Adsorption (TSA) can utilize low-grade thermal energy even from renewable energy source. At present, TSA technology still has several challenges to be practical application, such as intensive energy-consumption and low energy-efficiency. Thermodynamics could be a powerful method to explore the energy conversion mechanism of TSA, among which entropy analysis could further provide a clear picture on the irreversible loss, even with a possible strategy of energy-efficient improvement. Based on the theory of non-equilibrium thermodynamics, the entropy analysis of TSA cycle is conducted, using the Computational Fluid Dynamics (CFD) method. The physical model and conservation equations are established and calculation methods for entropy generation are presented as well. The entropy generation of each process in cycle is analyzed, and the influence from the main parameters of desorption process is presented with optimization analysis. Finally, the performance of the cycle with regeneration is compared with that of the cycle without regeneration, and the method of reducing the entropy generation is obtained as well. This paper provides possible directions of performance improvement of TSA cycle with regards on energy utilization efficiency and the reduction of irreversible loss.