Priority sources identification and risks assessment of heavy metal(loid)s in agricultural soils of a typical antimony mining watershed.

Heavy metal(loid) (HM) pollution in agricultural soils has become an environmental concern in antimony (Sb) mining areas. However, priority pollution sources identification and deep understanding of environmental risks of HMs face great challenges due to multiple and complex pollution sources coexist. Herein, an integrated approach was conducted to distinguish pollution sources and assess human health risk (HHR) and ecological risk (ER) in a typical Sb mining watershed in Southern China. This approach combines absolute principal component score-multiple linear regression (APCS-MLR) and positive matrix factorization (PMF) models with ER and HHR assessments. Four pollution sources were distinguished for both models, and APCS-MLR model was more accurate and plausible. Predominant HM concentration source was natural source (39.1%), followed by industrial and agricultural activities (23.0%), unknown sources (21.5%) and Sb mining and smelting activities (16.4%). Although natural source contributed the most to HM concentrations, it did not pose a significant ER. Industrial and agricultural activities predominantly contributed to ER, and attention should be paid to Cd and Sb. Sb mining and smelting activities were primary anthropogenic sources of HHR, particularly Sb and As contaminations. Considering ER and HHR assessments, Sb mining and smelting, and industrial and agricultural activities are critical sources, causing serious ecological and health threats. This study showed the advantages of multiple receptor model application in obtaining reliable source identification and providing better source-oriented risk assessments. HM pollution management, such as regulating mining and smelting and implementing soil remediation in polluted agricultural soils, is strongly recommended for protecting ecosystems and humans.

Simultaneous immobilization of multiple heavy metal(loid)s in contaminated water and alkaline soil inoculated Fe/Mn oxidizing bacterium.

Two strains of Fe/Mn oxidizing bacteria tolerant to high concentrations of multiple heavy metal(loid)s and efficient decontamination for them were screened. The surface of the bio-Fe/Mn oxides produced by the oxidation of Fe(II) and Mn(II) by Pseudomonas taiwanensis (marked as P4) and Pseudomonas plecoglossicida (marked as G1) contains rich reactive oxygen functional groups, which play critical roles in the removal efficiency and immobilization of heavy metal(loid)s in co-contamination system. The isolated strains P4 and G1 can grow well in the following environments: pH 5-9, NaCl 0-4%, and temperature 20-30°C. The removal efficiencies of Fe, Pb, As, Zn, Cd, Cu, and Mn are effective after inoculation of the strains P4 and G1 in the simulated water system (the initial concentrations of heavy metal(loid) were 1 mg/L), approximately reaching 96%, 92%, 85%, 67%, 70%, 54% and 15%, respectively. The exchangeable and carbonate bound As, Cd, Pb and Cu are more inclined to convert to the Fe-Mn oxide bound fractions in P4 and G1 treated soil, thereby reducing the phytoavailability and bioaccessible of heavy metal(loid)s. This research provides alternatives method to treat water and soil containing high concentrations of multi-heavy metal(loid)s.

Assessment of internal exposure risk from metals pollution of occupational and non-occupational populations around a non-ferrous metal smelting plant.

Non-ferrous metal smelting poses significant risks to public health. Specifically, the copper smelting process releases arsenic, a semi-volatile metalloid, which poses an emerging exposure risk to both workers and nearby residents. To comprehensively understand the internal exposure risks of metal(loid)s from copper smelting, we explored eighteen metal(loid)s and arsenic metabolites in the urine of both occupational and non-occupational populations using inductively coupled plasma mass spectrometry with high-performance liquid chromatography and compared their health risks. Results showed that zinc and copper (485.38 and 14.00 µg/L), and arsenic, lead, cadmium, vanadium, tin and antimony (46.80, 6.82, 2.17, 0.40, 0.44 and 0.23 µg/L, respectively) in workers (n=179) were significantly higher compared to controls (n=168), while Zinc, tin and antimony (412.10, 0.51 and 0.15 µg/L, respectively) of residents were significantly higher than controls. Additionally, workers had a higher monomethyl arsenic percentage (MMA%), showing lower arsenic methylation capacity. Source appointment analysis identified arsenic, lead, cadmium, antimony, tin and thallium as co-exposure metal(loid)s from copper smelting, positively relating to the age of workers. The hazard index (HI) of workers exceeded 1.0, while residents and control were approximately at 1.0. Besides, all three populations had accumulated cancer risks exceeding 1.0 × 10-4, and arsenite (AsIII) was the main contributor to the variation of workers and residents. Furthermore, residents living closer to the smelting plant had higher health risks. This study reveals arsenic exposure metabolites and multiple metals as emerging contaminants for copper smelting exposure populations, providing valuable insights for pollution control in non-ferrous metal smelting.

Investigation on cost-effective composites for CO2 adsorption from post-gasification residue and metal organic framework.

Cost-effective CO2 adsorbents are gaining increasing attention as viable solutions for mitigating climate change. In this study, composites were synthesized by electrochemically combining the post-gasification residue of Macadamia nut shell with copper benzene-1,3,5-tricarboxylate (CuBTC). Among the different composites synthesized, the ratio of 1:1 between biochar and CuBTC (B 1:1) demonstrated the highest CO2 adsorption capacity. Under controlled laboratory conditions (0°C, 1 bar, without the influence of ambient moisture or CO2 diffusion limitations), B 1:1 achieved a CO2 adsorption capacity of 9.8 mmol/g, while under industrial-like conditions (25°C, 1 bar, taking into account the impact of ambient moisture and CO2 diffusion limitations within a bed of adsorbent), it reached 6.2 mmol/g. These values surpassed those reported for various advanced CO2 adsorbents investigated in previous studies. The superior performance of the B 1:1 composite can be attributed to the optimization of the number of active sites, porosity, and the preservation of the full physical and chemical surface properties of both parent materials. Furthermore, the composite exhibited a notable CO2/N2 selectivity and improved stability under moisture conditions. These favorable characteristics make B 1:1 a promising candidate for industrial applications.

Ultrasonic humidifier aerosols: Observed high heavy metal enrichment and a new emission control method.

Ultrasonic humidifiers are commonly used in households to maintain indoor humidity and generate a large number of droplets or spray aerosols. However, there have been various health concerns associated with humidifier use, largely due to aerosols generated during operation. Here, we investigated the size distribution, chemical composition, and charged fraction of aerosol particles emitted from commercial ultrasonic humidifiers. Heavy metals in water used for humidifiers were found to be highly enriched in the ultrasonic humidifier aerosols (UHA), with the enrichment factors ranging from 102 to 107. This enrichment may pose health concerns for the building occupants, as UHA concentrations of up to 106 particles/cm3 or 3 mg/m3 were observed. Furthermore, approximately 90% of UHA were observed to be electrically charged, for the first time according to our knowledge. Based on this discovery, we proposed and tested a new method to remove UHA by using a simple electrical field. The designed electrical field in this work can efficiently remove 81.4% of UHA. Therefore, applying this electrical field could be an effective method to significantly reduce the health risks by UHA.

Synergistic effect of silicon availability and salinity on metal adsorption in a common estuarine diatom.

Increasing nitrogen and phosphorus discharge and decreasing sediment input have made silicon (Si) a limiting element for diatoms in estuaries. Disturbances in nutrient structure and salinity fluctuation can greatly affect metal uptake by estuarine diatoms. However, the combined effects of Si and salinity on metal accumulation in these diatoms have not been evaluated. In this study, we aimed to investigate how salinity and Si availability combine to influence the adsorption of metals by a widely distributed diatom Phaeodactylum tricornutum. Our data indicate that replete Si and low salinity in seawater can enhance cadmium and copper adsorption onto the diatom surface. At the single-cell level, surface potential was a dominant factor determining metal adsorption, while surface roughness also contributed to the higher metal loading capacity at lower salinities. Using a combination of non-invasive micro-test technology, atomic force microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, we demonstrate that the diversity and abundance of the functional groups embedded in diatom cell walls vary with salinity and Si supply. This results in a change in the cell surface potential and transient metal influx. Our study provides novel mechanisms to explain the highly variable metal adsorption capacity of a model estuarine diatom.

Adsorption removal of mercury from flue gas by metal selenide: A review.

Mercury (Hg) pollution has been a global concern in recent decades, posing a significant threat to entire ecosystems and human health due to its cumulative toxicity, persistence, and transport in the atmosphere. The intense interaction between mercury and selenium has opened up a new field for studying mercury removal from industrial flue gas pollutants. Besides the advantages of good Hg° capture performance and low secondary pollution of the mineral selenium compounds, the most noteworthy is the relatively low regeneration temperature, allowing adsorbent regeneration with low energy consumption, thus reducing the utilization cost and enabling recovery of mercury resources. This paper reviews the recent progress of mineral selenium compounds in flue gas mercury removal, introduces in detail the different types of mineral selenium compounds studied in the field of mercury removal, reviews the adsorption performance of various mineral selenium compounds adsorbents on mercury and the influence of flue gas components, such as reaction temperature, air velocity, and other factors, and summarizes the adsorption mechanism of different fugitive forms of selenium species. Based on the current research progress, future studies should focus on the economic performance and the performance of different carriers and sizes of adsorbents for the removal of Hg0 and the correlation between the gas-particle flow characteristics and gas phase mass transfer with the performance of Hg0 removal in practical industrial applications. In addition, it remains a challenge to distinguish the oxidation and adsorption of Hg0 quantitatively.

In-situ activation of biomimetic single-site bioorthogonal nanozyme for tumor-specific combination therapy.

Copper-catalyzed click chemistry offers creative strategies for activation of therapeutics without disrupting biological processes. Despite tremendous efforts, current copper catalysts face fundamental challenges in achieving high efficiency, atom economy, and tissue-specific selectivity. Herein, we develop a facile "mix-and-match synthetic strategy" to fabricate a biomimetic single-site copper-bipyridine-based cerium metal-organic framework (Cu/Ce-MOF@M) for efficient and tumor cell-specific bioorthogonal catalysis. This elegant methodology achieves isolated single-Cu-site within the MOF architecture, resulting in exceptionally high catalytic performance. Cu/Ce-MOF@M favors a 32.1-fold higher catalytic activity than the widely used MOF-supported copper nanoparticles at single-particle level, as first evidenced by single-molecule fluorescence microscopy. Furthermore, with cancer cell-membrane camouflage, Cu/Ce-MOF@M demonstrates preferential tropism for its parent cells. Simultaneously, the single-site CuII species within Cu/Ce-MOF@M are reduced by upregulated glutathione in cancerous cells to CuI for catalyzing the click reaction, enabling homotypic cancer cell-activated in situ drug synthesis. Additionally, Cu/Ce-MOF@M exhibits oxidase and peroxidase mimicking activities, further enhancing catalytic cancer therapy. This study guides the reasonable design of highly active heterogeneous transition-metal catalysts for targeted bioorthogonal reactions.

2D copper-iron bimetallic metal-organic frameworks for reduction of nitrate with boosted efficiency and ammonia selectivity.

Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy. Therefore, the method has received much attention. In this work, Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization. Bimetallic centers (Cu, Fe) with enhanced intrinsic activity demonstrated higher removal efficiency. Meanwhile, the 2D nanosheet reduced the mass transfer barrier between the catalyst and nitrate and increased the reaction kinetics. Therefore, the catalysts with a 2D structure showed much better removal efficiency than other structures (3D MOFs and Bulk MOFs). Under optimal conditions, Cu/Fe-2D MOF exhibited high nitrate removal efficiency (87.8%) and ammonium selectivity (89.3%) simultaneously. The ammonium yielded up to significantly 907.2 µg/(hr·mgcat) (7793.8 µg/(hr·mgmetal)) with Faradaic efficiency of 62.8% at an initial 100 mg N/L. The catalyst was proved to have good stability and was recycled 15 times with excellent effect. DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF. This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.

Tailored design of novel Co0-Coδ+ dual phase nanoparticles for selective CO2 hydrogenation to ethanol.

Catalytic hydrogenation of CO2 to ethanol is a promising solution to address the greenhouse gas (GHG) emissions, but many current catalysts face efficiency and cost challenges. Cobalt based catalysts are frequently examined due to their abundance, cost-efficiency, and effectiveness in the reaction, where managing the Co0 to Coδ+ ratio is essential. In this study, we adjusted support nature (Al2O3, MgO-MgAl2O4, and MgO) and reduction conditions to optimize this balance of Co0 to Coδ+ sites on the catalyst surface, enhancing ethanol production. The selectivity of ethanol reached 17.9% in a continuous flow fixed bed micro-reactor over 20 mol% Co@MgO-MgAl2O4 (CoMgAl) catalyst at 270 °C and 3.0 MPa, when reduced at 400 °C for 8 h. Characterisation results coupled with activity analysis confirmed that mild reduction condition (400 °C, 10% H2 balance N2, 8 h) with intermediate metal support interaction favoured the generation of partially reduced Co sites (Coδ+ and Co0 sites in single atom) over MgO-MgAl2O4 surface, which promoted ethanol synthesis by coupling of dissociative (CHx*)/non-dissociative (CHxO*) intermediates, as confirmed by density functional theory analysis. Additionally, the CoMgAl, affordably prepared through the coprecipitation method, offers a potential alternative for CO2 hydrogenation to yield valuable chemicals.

Impact of coking plant to heavy metal characteristics in groundwater of surrounding areas: Spatial distribution, source apportionment and risk assessments.

Coking industry is a potential source of heavy metals (HMs) pollution. However, its impacts to the groundwater of surrounding residential areas have not been well understood. This study investigated the pollution characteristics and health risks of HMs in groundwater nearby a typical coking plant. Nine HMs including Fe, Zn, Mo, As, Cu, Ni, Cr, Pb and Cd were analyzed. The average concentration of total HMs was higher in the nearby area (244.27 µg/L) than that of remote area away the coking plant (89.15 µg/L). The spatial distribution of pollution indices including heavy metal pollution index (HPI), Nemerow index (NI) and contamination degree (CD), all demonstrated higher values at the nearby residential areas, suggesting coking activity could significantly impact the HMs distribution characteristics. Four sources of HMs were identified by Positive Matrix Factorization (PMF) model, which indicated coal washing and coking emission were the dominant sources, accounted for 40.4%, and 31.0%, respectively. Oral ingestion was found to be the dominant exposure pathway with higher exposure dose to children than adults. Hazard quotient (HQ) values were below 1.0, suggesting negligible non-carcinogenic health risks, while potential carcinogenic risks were from Pb and Ni with cancer risk (CR) values > 10-6. Monte Carlo simulation matched well with the calculated results with HMs concentrations to be the most sensitive parameters. This study provides insights into understanding how the industrial coking activities can impact the HMs pollution characteristics in groundwater, thus facilitating the implement of HMs regulation in coking industries.

Efficacy and safety of a novel polytetrafluoroethylene-coated self-expandable metal stent for distal malignant biliary obstruction.

Background: Stent migration and sludge formation remain significant problems associated with covered self-expandable metal stents (CSEMSs). The EGIS biliary stent fully covered flare type (EGIS biliary stent), a new type of polytetrafluoroethylene-coated self-expandable metal stent with low axial force and an anti-migration system, was developed to overcome these disadvantages. We conducted this study to evaluate the efficacy and safety of this stent in comparison with conventional CSEMS (c-CSEMS). Methods: We retrospectively analyzed consecutive patients with unresectable pancreatic cancer who received initial CSEMS for distal malignant biliary obstruction. The primary outcome was time to recurrent biliary obstruction (RBO). Secondary outcomes included technical success rate, functional success rate, stent-related adverse events, causes of RBO, and re-intervention. Results: A total of 40 patients were included (EGIS group: 20; c-CSEMS group: 20). The technical and functional success rates were similar between the two groups. Stent-related adverse event rates (20% vs. 15%, p > 0.99) and overall RBO rates (56% vs. 50%, p > 0.99) were not significantly different between the two groups. Stent migration was the most common cause of RBO in the EGIS group, while stent occlusion was in the c-CSEMS group. The median time to RBO (102 vs. 434 days, p = 0.10) was not significantly different between the two groups. Endoscopic transpapillary re-intervention was successful in most patients in both groups. Conclusions: The EGIS biliary stent was not associated with a longer time to RBO compared to c-CSEMS. Further improvements, especially against stent migration, are needed to improve its efficacy.

A reliable method to prepare milligram size environmental samples to quantify metal(loid)s by high-resolution graphite furnace atomic absorption spectrometry.

We searched for an extraction method that would allow a precise quantification of metal(loid)s in milligram-size samples using high-resolution graphite furnace atomic absorption spectrometry (HR-GFAAS). We digested biological (DORM-4, DOLT-5 and TORT-3) and sediment (MESS-4) certified reference materials (CRMs) using nitric acid in a drying oven, aqua regia in a drying oven, or nitric acid in a microwave. In addition, we digested MESS-4 using a mixture of nitric and hydrofluoric acids in a drying oven. We also evaluated the effect of sample size (100 and 200 mg) on the extraction efficiency. Nitric acid extraction in a drying oven yielded the greatest recovery rates for all metal(loid)s in all tested CRMs (80.0 %-100.0 %) compared with the other extraction methods tested (67.3 %-99.2 %). In most cases, the sample size did not have a significant effect on the extraction efficiency. Therefore, we conclude that nitric acid digestion in a drying oven is a reliable extraction method for milligram-size samples to quantify metal(loid)s with HR-GFAAS. This validated method could provide substantial benefits to environmental quality monitoring programs by significantly reducing the time and costs required for sample collection, storage, transport and preparation, as well as the amount of hazardous chemicals used during sample extraction and analysis. •Sample digestion with nitric acid in a drying oven yielded the greatest recovery rates of metal(loid)s from biological and sediment certified reference materials.•The recovery rates of metal(loid)s from biological and sediment certified reference materials using nitric acid digestion in a drying oven ranged from 73 % to 100 %.•Digestion with nitric acid in a drying oven is a simple and reliable method to extract small size environmental samples for metal(loid)s quantification by high-resolution graphite furnace atomic absorption spectrometry.

Deciphering the molecular mechanisms underlying anti-pathogenic potential of a polyherbal formulation Enteropan® against multidrug-resistant Pseudomonas aeruginosa.

Objective: Anti-pathogenic potential of a polyherbal formulation Enteropan® was investigated against a multidrug-resistant strain of the bacterium Pseudomonas aeruginosa. Methods: Growth, pigment production, antibiotic susceptibility, etc., were assessed through appropriate in vitro assays. Virulence of the test pathogen was assessed employing the nematode worm Caenorhabditis elegans as a model host. Molecular mechanisms underlining the anti-pathogenic activity of the test formulation were elucidated through whole transcriptome analysis of the extract-exposed bacterial culture. Results: Enteropan-pre-exposed P. aeruginosa displayed reduced (~70%↓) virulence towards the model host C. elegans. Enteropan affected various traits like biofilm formation, protein synthesis and secretion, quorum-modulated pigment production, antibiotic susceptibility, nitrogen metabolism, etc., in this pathogen. P. aeruginosa could not develop complete resistance to the virulence-attenuating activity of Enteropan even after repeated exposure to this polyherbal formulation. Whole transcriptome analysis showed 17% of P. aeruginosa genome to get differentially expressed under influence of Enteropan. Major mechanisms through which Enteropan exerted its anti-virulence activity were found to be generation of nitrosative stress, oxidative stress, envelop stress, quorum modulation, disturbance of protein homeostasis and metal homeostasis. Network analysis of the differently expressed genes resulted in identification of 10 proteins with high network centrality as potential targets from among the downregulated genes. Differential expression of genes coding for five (rpoA, tig, rpsB, rpsL, and rpsJ) of these targets was validated through real-time polymerase chain reaction too, and they can further be pursued as potential targets by various drug discovery programmes.

Lithium Metal Recovery from Sea Water by a Flexible and Scalable Membrane with Lithium-Ion Exclusive Channels.

Sea water is abundant in lithium reserves, and extracting lithium metal from it holds the potential to not only mitigate the shortage of lithium in light of the fast-growing electric vehicle industry, but also serve as an anode electrode to provide electricity. The task, however, is challenging due to the harsh reactions and low lithium concentration in sea water. Here, we present a single-channel strategy based on a flexible and scalable lithium ion-sieve membrane for efficient lithium extraction. Our composite membrane exhibits high separation factor ßLi/Na of more than 2.87 × 107 with an ionic conductivity of 6.2×10-5 S cm-1. Lithium metal was electrolytically extracted from sea water through a hybrid-electrolyte system, which yielded a high Coulombic efficiency of 98.04% and a low energy consumption of 17.4 kWh kgLi-1 at an optimized extracting current of 200 µA cm-2. The extracted lithium metal can be directly integrated into a lithium-sulfur battery, delivering an energy output of 395 Wh kg-1. To demonstrate its industrial viability, we also fabricate a pouch cell with Li metal anode extracted by an amplified extraction prototype. This study has the potential to dispel concerns of lithium depletion and facilitate the sustainable development of lithium-based energy storage systems.

Metal-Phosphonate-Organic Network as Ion Enrichment Layer for Sustainable Zinc Metal Electrode with High Rate Capability.

Zinc (Zn) metal batteries could be the technology of choice for sustainable battery chemistries owing to its better safety and cost advantage. However, their cycle life and Coulombic efficiency (CE) are strongly limited by the dendritic growth and side reactions of Zn anodes. Herein, we proposed an in situ construction of a metal-phosphonate-organic network (MPON) with three-dimensional interconnected networks on Zn metal, which can act as an ion enrichment layer for Zn anodes in Zn-metal batteries. This MPON with abundant porous structure and phosphate sites possesses ion enriching properties and high Zn2+ transference number (0.83), which is beneficial for enhancing Zn2+ migration and self-concentrating kinetics. Meanwhile, MPON offers hydrophobicity to effectively inhibit the water-induced Zn anode corrosion. As a result, the Zn electrode exhibits superior Zn/Zn2+ reversibility of over 4 months at 3 mA cm-2 and a high CE of 99.6%. Moreover, the Zn/NaV3O8 ·1.5H2O and Zn/MnO2 full cells using ultrathin Zn anodes (10 µm) exhibit high-capacity retention of 81% and 78% after 1400 and 1000 cycles, respectively. This work provides a unique promise to design high-performance anode for practical Zn-metal-based batteries.

Oxyanion-Sensitive Catalytic Activity of Ni(II)/Oxyanion Systems for Heterogeneous Organic Degradation: Differential Oxidizing Capacity of Ni(III) and Ni(IV) as High-Valent Intermediates.

This study demonstrated that NiO and Ni(OH)2 as Ni(II) catalysts exhibited significant activity for organic oxidation in the presence of various oxyanions, such as hypochlorous acid (HOCl), peroxymonosulfate (PMS), and peroxydisulfate (PDS), which markedly contrasted with Co-based counterparts exclusively activating PMS to yield sulfate radicals. The oxidizing capacity of the Ni catalyst/oxyanion varied depending on the oxyanion type. Ni catalyst/PMS (or HOCl) degraded a broad spectrum of organics, whereas PDS enabled selective phenol oxidation. This stemmed from the differential reactivity of two high-valent Ni intermediates, Ni(III) and Ni(IV). A high similarity with Ni(III)OOH in a substrate-specific reactivity indicated the role of Ni(III) as the primary oxidant of Ni-activated PDS. With the minor progress of redox reactions with radical probes and multiple spectroscopic evidence on moderate Ni(III) accumulation, the significant elimination of non-phenolic contaminants by NiOOH/PMS (or HOCl) suggested the involvement of Ni(IV) in the substrate-insensitive treatment capability of Ni catalyst/PMS (or HOCl). Since the electron-transfer oxidation of organics by high-valent Ni species involved Ni(II) regeneration, the loss of the treatment efficiency of Ni/oxyanion was marginal over multiple catalytic cycles.

2D coordination polymers of cadmium(II) and zinc(II) derived from N,N'-bis(glycinyl)pyromellitic diimide: microwave-assisted synthesis, structures, spectroscopic properties and influence of metal-ion size.

Two new two-dimensional (2D) coordination polymers (CPs), namely, poly[diaqua[µ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O''']cadmium(II)], [Cd(C14H6N2O8)(H2O)2]n (1), and poly[[tetraaqua[µ4-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ4O:O':O'':O'''][µ2-2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetato-κ2O:O']dizinc(II)] dihydrate], {[Zn(C14H6N2O8(H2O)2]·H2O}n (2), have been synthesized by the microwave-irradiated reaction of Cd(CH3COO)2·2H2O and Zn(CH3COO)2·2H2O, respectively, with N,N'-bis(glycinyl)pyromellitic diimide {BGPD, namely, 2,2'-(1,3,5,7-tetraoxo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-2,6-diyl)diacetic acid, H2L}. In the crystal structure of 1, the CdII ion is six-coordinated by four carboxylate O atoms from four symmetry-related L2- dianions and two coordinated water molecules, furnishing an octahedral coordination geometry. The bridging L2- dianion links four symmetry-related CdII cations into a 2D layer-like structure with a 3,4-connected bex topology. In the crystal structure of 2, the ZnII ion is five-coordinated by three carboxylate O atoms from three different L2- dianions and two coordination water molecules, furnishing a trigonal bipyramidal coordination geometry. Two crystallographically independent ligands serve as µ4- and µ2-bridges, respectively, to connect the ZnII ions, thereby forming a 2D layer with a 3,3-connected hcb topology. Crystal structure analysis reveals the presence of n→π* interactions between two carbonyl groups of the pyromellitic diimide moieties in 1 and 2. CP 1 exhibits an enhanced fluorescence emission compared with free H2L. The framework of 2 decomposes from 720 K, indicating its high thermal stability. A comparative analysis of a series of structures based on the BGPD ligand indicates that the metal-ion size has a great influence on the connection modes of the metal ions due to different steric effects, which, in turn, affects the structures of the SBUs (secondary building units) and frameworks.

Advancements in Atomically Precise Nanocluster Protected by Thiacalix[4]arene.

Coinage metal nanoclusters (NCs), comprising a few to several hundred atoms, are prized for their size-dependent properties crucial in catalysis, sensing, and biomedicine. However, their practical application is often hindered by stability and reactivity challenges. Thiacalixarene, a macrocyclic ligand, shows promise in stabilizing silver, copper, and bimetallic NCs, enhancing their structural integrity and chemical stability. This investigation delves into the unique properties of thiacalix[4]arene and their role in bolstering NC stability, catalytic efficiency, and sensing capabilities. The current challenges and future prospects are critically evaluated, underscoring the transformative impact of thiacalix[4]arene in nanoscience. This review aims to broaden the utilization of atomically precise coinage metal NCs, unlocking new avenues across scientific and industrial applications.

Co-treatment of municipal solid waste incineration fly ash and alumina-/silica-containing waste: A critical review.

Municipal solid waste incineration fly ash (MSWI-FA) is a hazardous by-product of the incineration process, characterized by elevated levels of heavy metals, chlorides, and dioxins. With a composition high in calcium but low in silicon/aluminum, MSWI-FA exhibits a poor immobilization effect, high energy demands, and limited pozzolanic activity when it is disposed of or reutilized alone. Conversely, alumina-/silica-containing waste (ASW) presents a chemical composition rich in SiO2 and/or Al2O3, offering an opportunity for synergistic treatment with MSWI-FA to facilitate its harmless disposal and resource recovery. Despite the growing interest in co-treatment of MSWI-FA and ASW in recent years, a comprehensive evaluation of ASW's roles in this process remains absent from the existing literature. Therefore, this study endeavors to examine the advancement in the co-treatment of MSWI-FA and ASW, with the focus on three key aspects, i.e., elucidating the immobilization mechanisms by which ASW improves the solidification/stabilization of MSWI-FA, exploring the synergies between MSWI-FA and ASW in various thermal and mechanochemical treatments, and highlighting the benefits of incorporating ASW in the production of MSWI-FA-based building materials. Additionally, in the pursuit of sustainable solid waste management, this review identifies research gaps and delineates future prospects for the co-treatment of MSWI-FA and ASW.