A vertically-stacked MXene/rGO composite membrane for highly efficient H2/CO2 separation.

A vertically-stacked MXene/rGO composite membrane with ultrashort transport channels is reported here, which demonstrated outstanding molecular sieving, i.e., H2/CO2 selectivity of up to 83 together with high H2 permeance of 2.7 × 10-7 mol m-2 s-1 Pa-1 at 120 °C, highlighting its applicability for H2/CO2 separation in CO2 capture and sequestration.

Association between serum 25-hydroxyvitamin D and vitamin D dietary supplementation and risk of all-cause and cardiovascular mortality among adults with hypertension.

BACKGROUND: The relationship between vitamin D status and mortality among adults with hypertension remains unclear. METHODS: This prospective cohort study involved a sample of 19,500 adults with hypertension who participated in the National Health and Nutrition Examination Survey (NHANES) from 2001 to 2018. We utilized a weighted COX proportional hazard model to assess the association between vitamin D status and mortality. This statistical model calculates hazard ratios (HR) and their corresponding 95% confidence intervals (95% CI). RESULTS: The study indicated that lower serum 25(OH)D concentration was associated with an increased risk of all-cause mortality among individuals with hypertension. Specially. Those with concentrations between 25.0 and 49.9 nmol/L (HR = 1.71, 95%CI = 1.22-2.40) and less than 25.0 nmol/L (HR = 1.97, 95%CI = 1.15-3.39) had higher hazard ratios for all-cause mortality. Individuals with hypertension who took vitamin D supplements had a lower risk of all-cause mortality, but not the risk of CVD mortality (HR 0.75, 95%CI 0.54-1.03), compared to those who did not supplement (HR = 0.76, 95%CI = 0.61-0.94). Subgroup analysis further revealed that vitamin D supplementation was associated with a reduced risk of all-cause mortality among individuals without diabetes (HR = 0.65, 95%CI = 0.52-0.81) and individuals without CVD (HR = 0.75, 95%CI = 0.58-0.97), and a decreased risk of CVD mortality among individuals without diabetes (HR = 0.63, 95%CI = 0.45-0.88) and without CVD (HR = 0.61, 95%CI = 0.40-0.92). Furthermore, higher-dose vitamin D supplementation was also associated with a greater reduction in all-cause mortality among hypertensive individuals, and there was the potential synergistic effect of combining normal-dose calcium and vitamin D supplementation, showing a superior effect on mortality compared to low-dose supplementation in adults with hypertension. CONCLUSIONS: This prospective cohort study demonstrated a significant association between lower serum 25 (OH)D concentration and increased all-cause mortality among adults with hypertension. Furthermore, the study found that vitamin D supplementation had a strong and significantly positive correlation with reduced all-cause and CVD mortality among hypertensive individuals without diabetes or CVD. This positive correlation suggests that vitamin D supplementation could potentially be an effective strategy to reduce the risk of mortality in this specific group of people.

Bromide triggers efficient peroxymonosulfate activation for phosphonate degradation.

Phosphonates have received a widespread attention in wastewater treatment due to their potential threat to the water environment. Advanced oxidation processes (AOPs) are feasible methods to degrade phosphonates, and most of the coexisting substances in water show a negative factor during their oxidation. However, the effect of bromide (Br-) on the degradation of phosphonates in peroxymonosulfate (PMS) activation is still unclear. Herein, using 1-hydroxyethane 1,1-diphosphonic acid (HEDP) as a target phosphonate, Br- could remarkably enhance the degradation of HEDP in PMS activation compared to the PMS alone. Under the condition of pH = 7.0, the optimal degradation efficiency of HEDP is 84.8% in the PMS/Br- process after 30-min reaction, whereas no significant oxidation is obtained in the PMS/I- and PMS/Cl- processes. Multiple experiments (i.e., electron paramagnetic resonance (EPR), radical quenching experiments and chemical probs) confirm that free bromine, SO4•- and HO• paly a minor role in HEDP removal, and bromine radical species make a dominant responsible for HEDP oxidation. Additionally, NO3-, SO42-, Cl-, and HCO3- have a little effect on the degradation of HEDP, but the HEDP removal is greatly inhibited in the presence of humic acid (HA). However, the degradation efficiency of HEDP using PMS/Br- process in river and sewage is a much higher than UV/persulfate (PDS) and UV/H2O2 processes. This study provides a new sight into the effect of Br- on the degradation phosphonates in PMS activation process.

Recent Progress on Nickel- and Iron-Based Metallic Organic Frameworks for Oxygen Evolution Reaction: A Review.

Developing sustainable energy solutions to safeguard the environment is a critical ongoing demand. Electrochemical water splitting (EWS) is a green approach to create effective and long-lasting electrocatalysts for the water oxidation process. Metal organic frameworks (MOFs) have become commonly utilized materials in recent years because of their distinguishing pore architectures, metal nodes easy accessibility, large specific surface areas, shape, and adaptable function. This review outlines the most significant developments in current work on developing improved MOFs for enhancing EWS. The benefits and drawbacks of MOFs are first discussed in this review. Then, some cutting-edge methods for successfully modifying MOFs are also highlighted. Recent progress on nickel (Ni) and iron (Fe) based MOFs have been critically discussed. Finally, a comprehensive analysis of the existing challenges and prospects for Ni- and Fe-based MOFs are summarized.

Fabricating an adsorbent and micro-nano bubble catalyst through confining maghemite in the ß cage of NaY zeolite.

This work reports the ion exchange fabrication of maghemite (γ-Fe2O3) modified NaY zeolite (Fe2O3@Y) with bifunction of adsorption and catalysis. The Fe3+ successfully replaced the Na+ in the ß cage of zeolite in the ion exchange process and coordinated with framework oxygens to form magnetic γ-Fe2O3. Therefore, most of the γ-Fe2O3 particles were confined in the ß cages, which resulted in the high dispersal and stability of the catalyst. The Fe2O3@Y could remove methylene blue (MB) model pollutants up to 59.02 and 61.47% through the adsorption and catalysis process, respectively. The hydrogen bond between the OH- ions around the Fe2O3@Y surface and the N and O presented in the MB molecules enabled the chemical adsorption to MB, which accorded with the pseudo-second-order kinetic model. Further, the H+ existed in the solution and the ß cage of zeolite promoted the collapse of micro-nano bubbles (MNBs). Then, the γ-Fe2O3 catalyst would be activated by high temperature and oxidated OH- to produce hydroxyl radicals for pollutant degradation. Thus, pollutant removal was attributed to the combined effects of adsorption and catalysis in the Fe2O3@Y + MNB system. In this work, the Fe2O3@Y was demonstrated as a potentially magnetic adsorbent or MNB catalyst for wastewater treatment.

Dormancy and double-activation strategy for construction of high-performance mixed-matrix membranes.

Mixed-matrix membranes (MMMs) have the potential for energy-efficient gas separation by matching the superior mass transfer and anti-plasticization properties of the fillers with processability and scaling up features of the polymers. However, construction of high-performance MMMs has been prohibited due to low filler-loading and the existence of interfacial defects. Here, high MOF-loaded, i.e., 55 wt %, MMMs are developed by a 'dormancy and double-activation' (DDA) strategy. High MOF precursor concentration suppresses crystallization in the membrane casting solution, realizing molecular level mixing of all components. Then, the polymeric matrix was formed with uniform encapsulation of MOF nutrients. Subsequently, double-activation was employed to induce MOF crystallization: the alkali promotes MOFs nucleation to harvest small porous nanocrystals while excessive ligands activate the metal ions to enhance the MOFs conversion. As such, quasi-semi-continuous mass transfer channels can be formed in the MMMs by the connected MOFs nanocrystals to boost the gas permeability. The optimized MMM shows significantly ameliorated CO2 permeability, i.e., 2841 Barrer, five-fold enhancement compared with pristine polymer membrane, with a good CO2 /N2 selectivity of 36. Besides, the nanosized MOFs intensify their interaction with polymer chains, endowing the MMMs with good anti-plasticization behaviour and stability, which advances practical application of MMMs in carbon capture.

Hierarchical Hollow Carbon Particles with Encapsulation of Carbon Nanotubes for High Performance Supercapacitors.

A novel and sustainable carbon-based material, referred to as hollow porous carbon particles encapsulating multi-wall carbon nanotubes (MWCNTs) (CNTs@HPC), is synthesized for use in supercapacitors. The synthesis process involves utilizing LTA zeolite as a rigid template and dopamine hydrochloride (DA) as the carbon source, along with catalytic decomposition of methane (CDM) to simultaneously produce MWCNTs and COx -free H2 . The findings reveal a distinctive hierarchical porous structure, comprising macropores, mesopores, and micropores, resulting in a total specific surface area (SSA) of 913 m2  g-1 . The optimal CNTs@HPC demonstrates a specific capacitance of 306 F g-1 at a current density of 1 A g-1 . Moreover, this material demonstrates an electric double-layer capacitor (EDLC) that surpasses conventional capabilities by exhibiting additional pseudocapacitance characteristics. These properties are attributed to redox reactions facilitated by the increased charge density resulting from the attraction of ions to nickel oxides, which is made possible by the material's enhanced hydrophilicity. The heightened hydrophilicity can be attributed to the presence of residual silicon-aluminum elements in CNTs@HPC, a direct outcome of the unique synthesis approach involving nickel phyllosilicate in CDM. As a result of this synthesis strategy, the material possesses excellent conductivity, enabling rapid transportation of electrolyte ions and delivering outstanding capacitive performance.

Oral Nanomedicine: Challenges and Opportunities.

Compared to injection administration, oral administration is free of discomfort, wound infection, and complications and has a higher compliance rate for patients with diverse diseases. However, oral administration reduces the bioavailability of medicines, especially biologics (e.g., peptides, proteins, and antibodies), due to harsh gastrointestinal biological barriers. In this context, the development and prosperity of nanotechnology have helped improve the bioactivity and oral availability of oral medicines. On this basis, first, the biological barriers to oral administration are discussed, and then oral nanomedicine based on organic and inorganic nanomaterials and their biomedical applications in diverse diseases are reviewed. Finally, the challenges and potential opportunities in the future development of oral nanomedicine, which may provide a vital reference for the eventual clinical transformation and standardized production of oral nanomedicine, are put forward.

Protein-activated atomic layer deposition for robust crude-oil-repellent hierarchical nano-armored membranes.

Atomic layer deposition (ALD) offers unique capabilities to fabricate atomically engineered porous materials with precise pore tuning and multi-functionalization for diverse applications like advanced membrane separations towards sustainable energy-water systems. However, current ALD technique is inhibited on most non-polar polymeric membranes due to lack of accessible nucleation sites. Here, we report a facile method to efficiently promote ALD coating on hydrophobic surface of polymeric membranes via novel protein activation/sensitization. As a proof of concept, TiO2 ALD-coated membranes activated by bovine serum albumin exhibit remarkable superhydrophilicity, ultralow underwater crude oil adhesion, and robust tolerance to rigorous environments including acid, alkali, saline, and ethanol. Most importantly, excellent cyclable crude oil-in-water emulsion separation performance can be achieved. The mechanism for activation/sensitization is rooted in reactivity for a particular set of amino acids. Furthermore, the universality of protein-sensitized ALD is demonstrated using common egg white, promising numerous potential usages in biomedical engineering, environmental remediation, low-carbon manufacturing, catalysis, and beyond.

Single atom manganese catalyst boosting selective oxidation of alcohols with activated peroxymonosulfate.

Selective oxidations are important reactions in organic synthesis for fine chemical industry and conventional methods are expensive and produce a lot of toxic wastes. Herein, we demonstrate a facile and environmentally benign technique for liquid phase selective oxidation based on graphene-supported Mn single-atom-catalyst (SAMn-G) for efficient peroxymonosulfate (PMS) activation. The active Mn component in the developed SAMn-G catalyst reached single-atomic dispersion on graphene substrate via the coordination of individual Mn atoms with the doped N from the graphene framework. SAMn-G activated PMS via a nonradical-dominated pathway, which could convert aromatic alcohols into aldehydes or ketones at a mild temperature. The SAMn-G catalyst exhibited superior conversion and aldehyde selectivity in alcohol oxidation in comparison with their counterpart catalysts possessing either homogeneous Mn ions or oxide particles. The high activation efficiency of SAMn-G is due to the synergistic effect between Mn atoms and graphene substrate, as well as the dominated reaction pathway from nonradical oxidation, which is more selective than these free radicals to oxidize the alcohols. Concerted experimental evidence indicates that the non-radical oxidation process was highly possible to follow the electron transfer mechanism by PMS/organic adsorption on the surface of the catalyst. This study provides a fundamental understanding of PMS activation mediated by single atom catalyst for organic synthesis and the achieved insights can also help the catalyst design for other liquid phase selective oxidation processes.

Ice-confined synthesis of highly ionized 3D-quasilayered polyamide nanofiltration membranes.

Existing polyamide (PA) membrane synthesis protocols are underpinned by controlling diffusion-dominant liquid-phase reactions that yield subpar spatial architectures and ionization behavior. We report an ice-confined interfacial polymerization strategy to enable the effective kinetic control of the interfacial reaction and thermodynamic manipulation of the hexagonal polytype (Ih) ice phase containing monomers to rationally synthesize a three-dimensional quasilayered PA membrane for nanofiltration. Experiments and molecular simulations confirmed the underlying membrane formation mechanism. Our ice-confined PA nanofiltration membrane features high-density ionized structure and exceptional transport channels, realizing superior water permeance and excellent ion selectivity.

Nanoparticle (NP)-mediated APOC1 silencing to inhibit MAPK/ERK and NF-κB pathway and suppress breast cancer growth and metastasis.

Breast cancer is one of the most common malignant tumors with high mortality and poor prognosis in women. There is an urgent need to discover new therapeutic targets for breast cancer metastasis. Herein, we identified that Apolipoprotein C1 (APOC1) was up-regulated in primary tumor of breast cancer patient that recurrence and metastasis by immunohistochemistry (IHC). Kaplan-Meier Plotter database showed that high levels of APOC1 in breast cancer patients were strongly associated with worse overall survival (OS) and relapse-free survival (RFS). Mechanistically, APOC1 silencing significantly inhibits MAPK/ERK kinase pathway and restrains the NF-κB to decrease the transcription of target genes related to growth and metastasis in vitro. Based on this regulatory mechanism, we developed these findings into potential therapeutic drugs, glutathione (GSH) responsive nano-particles (NPs) were used for systemic APOC1 siRNA delivery, NPs (siAPOC1) silenced APOC1 expression, and subsequently resulted in positive anti-tumor effects in orthotopic and liver metastasis models in vivo. Taken together, GSH responsive NP-mediated siAPOC1 delivery was proved to be effective in regulating growth and metastasis in multiple tumor models. These findings show that APOC1 could be a potential biomarker to predict the prognosis of breast cancer patients and NP-mediated APOC1 silencing could be new strategies for exploration of new treatments for breast cancer metastasis.

Changes in microbial community during hydrolyzed sludge reduction.

In this study, the effects of different enzymes (lysozyme, α-amylase and neutral protease) on sludge hydrolysis efficiency and microbial community in sequencing batch reactor (SBR) were introduced. The results showed that the hydrolysis efficiencies of the three enzymes were 48.5, 22.5 and 31%, respectively, compared with the accumulated sludge discharge of the blank control group. However, it has varying degrees of impact on the effluent quality, and the denitrification and phosphorus removal effect of the system deteriorates. The lysozyme that achieves the optimal sludge hydrolysis effect of 48.5% has the greatest impact on the chemical oxygen demand (COD), total nitrogen (TN), and nitrate nitrogen (NO3--N) of the effluent. The sludge samples of the control group and the groups supplemented with different enzyme preparations were subjected to high-throughput sequencing. It was found that the number of OTUs (Operational Taxonomic Units) of the samples was lysozyme > α-amylase > blank control > neutral protease. Moreover, the abundance grade curve of the sludge samples supplemented with lysozyme and α-amylase was smoother, and the community richness and diversity were improved by lysozyme and α-amylase. The species diversity of the sludge supplemented with lysozyme and neutral protease was great, and the community succession was obvious. The introduction of enzymes did not change the main microbial communities of the sludge, which were mainly Proteobacteria, Actinobacteria and Bacteroidetes. The effects of three enzyme preparations on sludge reduction and microbial diversity during pilot operation were analyzed, the gap in microbial research was filled, which provided theoretical value for the practical operation of enzymatic sludge reduction.

Pt-Loaded Nb─W Metal Composite Oxide for Selective Cleavage of Secondary C─O Bonds.

Selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) is recognized as one of the most promising reactions for the valorization of biomass. Precise activation of C─O bonds of glycerol molecule is the key step to realize the high yield of catalytic conversion. Here, a Pt-loaded Nb-W composite oxides with crystallographic shear phase for the precise activation and cleavage of secondary C─O (C(2)─O) bonds are first reported. The developed Nb14 W3 O44 with uniform structure possesses arrays of W-O-Nb active sites that totally distinct from individual WOx or NbOx species, which is superior to the adsorption and activation of C(2)─O bonds. The Nb14 W3 O44 support with rich reversible redox couples also promotes the electron feedback ability of Pt and enhances its interaction with Pt nanoparticles, resulting in high activity for H2 dissociation and hydrogenation. All these favorable factors confer the Pt/Nb14 W3 O44 excellent performance for selective hydrogenolysis of glycerol to 1,3-PDO with the yield of 75.2% exceeding the record of 66%, paying the way for the commercial development of biomass conversion. The reported catalysts or approach can also be adopted to create a family of Nb-W metal composite oxides for other catalytic reactions requiring selective C─O bond activation and cleavage.

Isotherm data for adsorption of amoxicillin, ampicillin, and doripenem onto bentonite.

The dataset reported in this article describes the adsorption isotherms of amoxicillin, ampicillin, and doripenem onto bentonite. Batch adsorption experiments were carried out on single antibiotic solutions with various dosage of bentonite across temperatures from 30 to 50 °C. The adsorbent loading dataset was later obtained by measuring the concentration of antibiotic solution at adsorption equilibrium via UV-Vis spectrophotometer. The dataset was also fitted using various isotherm models including Freundlich, Langmuir, Toth, Hill, and Dubinin-Radushkevich models to further analyze the adsorption behavior. On top of that, orthogonal regression was applied to avoid fitting biasness, whereby the fitting results revealed the highest adsorption capacities of 82.259 mg g-1 for amoxicillin, 78.851 mg g-1 for ampicillin, and 93.278 mg g-1 for doripenem using Langmuir model, which gave an accurate representation of the adsorption isotherm dataset that was consistent with the results of Toth and Hill model.

Ultra-Permeable Dual-Mechanism-Driven Graphene Oxide Framework Membranes for Precision Ion Separations.

Two-dimensional graphene oxide (GO) membranes are gaining popularity as a promising means to address global water scarcity. However, current GO membranes fail to sufficiently exclude angstrom-sized ions from solution. Herein, a de novo "posterior" interfacial polymerization (p-IP) strategy is reported to construct a tailor-made polyamide (PA) network in situ in an ultrathin GO membrane to strengthen size exclusion while imparting a positively charged membrane surface to repel metal ions. The electrostatic repulsion toward metal ions, coupled with the reinforced size exclusion, synergistically drives the high-efficiency metal ion separation through the synthesized positively charged GO framework (PC-GOF) membrane. This dual-mechanism-driven PC-GOF membrane exhibits superior metal ion rejection, anti-fouling ability, good operational stability, and ultra-high permeance (five times that of pristine GO membranes), enabling a sound step towards a sustainable water-energy-food nexus.

Boosting membrane carbon capture via multifaceted polyphenol-mediated soldering.

Advances in membrane technologies are significant for mitigating global climate change because of their low cost and easy operation. Although mixed-matrix membranes (MMMs) obtained via the combination of metal-organic frameworks (MOFs) and a polymer matrix are promising for energy-efficient gas separation, the achievement of a desirable match between polymers and MOFs for the development of advanced MMMs is challenging, especially when emerging highly permeable materials such as polymers of intrinsic microporosity (PIMs) are deployed. Here, we report a molecular soldering strategy featuring multifunctional polyphenols in tailored polymer chains, well-designed hollow MOF structures, and defect-free interfaces. The exceptional adhesion nature of polyphenols results in dense packing and visible stiffness of PIM-1 chains with strengthened selectivity. The architecture of the hollow MOFs leads to free mass transfer and substantially improves permeability. These structural advantages act synergistically to break the permeability-selectivity trade-off limit in MMMs and surpass the conventional upper bound. This polyphenol molecular soldering method has been validated for various polymers, providing a universal pathway to prepare advanced MMMs with desirable performance for diverse applications beyond carbon capture.

Rod-Like Nanostructured Cu-Co Spinel with Rich Oxygen Vacancies for Efficient Electrocatalytic Dechlorination.

Dichloromethane (CH2Cl2) hydrodechlorination to methane (CH4) is a promising approach to remove the halogenated contaminants and generate clean energy. In this work, rod-like nanostructured CuCo2O4 spinels with rich oxygen vacancies are designed for highly efficient electrochemical reduction dechlorination of dichloromethane. Microscopy characterizations revealed that the special rod-like nanostructure and rich oxygen vacancies can efficiently enhance surface area, electronic/ionic transport, and expose more active sites. The experimental tests demonstrated that CuCo2O4-3 with rod-like nanostructures outperformed other morphology of CuCo2O4 spinel nanostructures in catalytic activity and product selectivity. The highest methane production of 148.84 µmol in 4 h with a Faradaic efficiency of 21.61% at -2.94 V (vs SCE) is shown. Furthermore, the density function theory proved oxygen vacancies significantly decreased the energy barrier to promote the catalyst in the reaction and Ov-Cu was the main active site in dichloromethane hydrodechlorination. This work explores a promising way to synthesize the highly efficient electrocatalysts, which may be an effective catalyst for dichloromethane hydrodechlorination to methane.

Effect of Cu-Doped Co-Mn Spinel for Boosting Low-Temperature NO Reduction by CO: Exploring the Structural Properties, Performance, and Mechanisms.

Cobalt-manganese spinel catalysts performed unsatisfactory activity at low-temperature and narrow reaction temperature window, which greatly limited the application in NO reduction by CO. Herein, we synthesize a series of Cu-doped CoMn2O4 catalysts and apply to NO reduction by CO. The Cu0.3Co0.7Mn2O4 exhibited superior catalytic performance, reaching 100% NO conversion and 80% N2 selectivity at 250 °C. Detailed structural analysis showed that the introduced Cu replaces some Co in tetrahedral coordination to induce a strong synergistic effect between different metals. This endows the catalyst with the promotion of both electron transfer and oxygen vacancy generation on the catalyst surface. Importantly, the reaction mechanism and pathway were further revealed by in situ diffusion Fourier transform infrared spectroscopy (DRIFTS) and density functional theory (DFT) calculations. The results indicated that the cycle of oxygen vacancy mainly determines the catalytic activity of NO reduction by CO. Notably, Cu doping significantly lowered the energy barrier of the rate-determining step (*CO + O → *Ov + CO2), facilitating the desorption of the CO2 and exposing the active sites for efficient NO reduction with CO. This work offers an effective way for designing the catalyst in NO reduction by CO and provides a reference for exploring the catalytic mechanism of the reaction.

Polyamide membranes with nanoscale ordered structures for fast permeation and highly selective ion-ion separation.

Fast permeation and effective solute-solute separation provide the opportunities for sustainable water treatment, but they are hindered by ineffective membranes. We present here the construction of a nanofiltration membrane with fast permeation, high rejection, and precise Cl-/SO42- separation by spatial and temporal control of interfacial polymerization via graphitic carbon nitride (g-C3N4). The g-C3N4 nanosheet binds preferentially with piperazine and tiles the water-hexane interface as revealed by molecular dynamics studies, thus lowering the diffusion rate of PIP by one order of magnitude and restricting its diffusion pathways towards the hexane phase. As a result, membranes with nanoscale ordered hollow structure are created. Transport mechanism across the structure is clarified using computational fluid dynamics simulation. Increased surface area, lower thickness, and a hollow ordered structure are identified as the key contributors to the water permeance of 105 L m2·h-1·bar-1 with a Na2SO4 rejection of 99.4% and a Cl-/SO42- selectivity of 130, which is superior to state-of-the-art NF membranes. Our approach for tuning the membrane microstructure enables the development of ultra-permeability and excellent selectivity for ion-ion separation, water purification, desalination, and organics removal.