Understanding the role of transition metal single-atom electronic structure in oxysulfur radical-mediated oxidative degradation.

The ubiquity of refractory organic matter in aquatic environments necessitates innovative removal strategies. Sulfate radical-based advanced oxidation has emerged as an attractive solution, offering high selectivity, enduring efficacy, and anti-interference ability. Among many technologies, sulfite activation, leveraging its cost-effectiveness and lower toxicity compared to conventional persulfates, stands out. Yet, the activation process often relies on transition metals, suffering from low atom utilization. Here we introduce a series of single-atom catalysts (SACs) employing transition metals on g-C3N4 substrates, effectively activating sulfite for acetaminophen degradation. We highlight the superior performance of Fe/CN, which demonstrates a degradation rate constant significantly surpassing those of Ni/CN and Cu/CN. Our investigation into the electronic and spin polarization characteristics of these catalysts reveals their critical role in catalytic efficiency, with oxysulfur radical-mediated reactions predominating. Notably, under visible light, the catalytic activity is enhanced, attributed to an increased generation of oxysulfur radicals and a strengthened electron donation-back donation dynamic. The proximity of Fe/CN's d-band center to the Fermi level, alongside its high spin polarization, is shown to improve sulfite adsorption and reduce the HOMO-LUMO gap, thereby accelerating photo-assisted sulfite activation. This work advances the understanding of SACs in environmental applications and lays the groundwork for future water treatment technologies.

Postbiotics in rheumatoid arthritis: emerging mechanisms and intervention perspectives.

Rheumatoid arthritis (RA) is a prevalent chronic autoimmune disease that affects individuals of all age groups. Recently, the association between RA and the gut microbiome has led to the investigation of postbiotics as potential therapeutic strategies. Postbiotics refer to inactivated microbial cells, cellular components, or their metabolites that are specifically intended for the microbiota. Postbiotics not only profoundly influence the occurrence and development of RA, but they also mediate various inflammatory pathways, immune processes, and bone metabolism. Although they offer a variety of mechanisms and may even be superior to more conventional "biotics" such as probiotics and prebiotics, research on their efficacy and clinical significance in RA with disruptions to the intestinal microbiota remains limited. In this review, we provide an overview of the concept of postbiotics and summarize the current knowledge regarding postbiotics and their potential use in RA therapy. Postbiotics show potential as a viable adjunctive therapy option for RA.

Homogeneous Vacancies-Enhanced Orbital Hybridization for Selective and Efficient CO2-to-CO Electrocatalysis.

Crafting vacancies offers an efficient route to upgrade the selectivity and productivity of nanomaterials for CO2 electroreduction. However, defective nanoelectrocatalysts bear catalytically active vacancies mostly on their surface, with the rest of the interior atoms adiaphorous for CO2-to-product conversion. Herein, taking nanosilver as a prototype, we arouse the catalytic ability of internal atoms by creating homogeneous vacancies realized via electrochemical reconstruction of silver halides. The homogeneous vacancies-rich nanosilver, compared to the surface vacancies-dominated counterpart, features a more positive d-band center to trigger an intensified hybridization of the Ag_d orbital with the C_P orbital of the *COOH intermediate, leading to an accelerated CO2-to-CO transformation. These structural and electronic merits allow a large-area (9 cm-2) electrode to generate nearly pure CO with a CO/H2 Faradaic efficiency ratio of 6932 at an applied current of 7.5 A. These findings highlight the potential of designing new-type defects in realizing the industrialization of electrocatalytic CO2 reduction.

Triangle Cl-Ag1 -Cl Sites for Superior Photocatalytic Molecular Oxygen Activation and NO Oxidation of BiOCl.

BiOCl photocatalysis shows great promise for molecular oxygen activation and NO oxidation, but its selective transformation of NO to immobilized nitrate without toxic NO2 emission is still a great challenge, because of uncontrollable reaction intermediates and pathways. In this study, we demonstrate that the introduction of triangle Cl-Ag1 -Cl sites on a Cl-terminated, (001) facet-exposed BiOCl can selectively promote one-electron activation of reactant molecular oxygen to intermediate superoxide radicals (⋅O2 - ), and also shift the adsorption configuration of product NO3 - from the weak monodentate binding mode to a strong bidentate mode to avoid unfavorable photolysis. By simultaneously tuning intermediates and products, the Cl-Ag1 -Cl-landen BiOCl achieved >90 % NO conversion to favorable NO3 - of high selectivity (>97 %) in 10 min under visible light, with the undesired NO2 concentration below 20 ppb. Both the activity and the selectivity of Cl-Ag1 -Cl sites surpass those of BiOCl surface sites (38 % NO conversion, 67 % NO3 - selectivity) or control O-Ag1 -O sites on a benchmark photocatalyst P25 (67 % NO conversion and 87 % NO3 - selectivity). This study develops new single-atom sites for the performance enhancement of semiconductor photocatalysts, and also provides a facile pathway to manipulate the reactive oxygen species production for efficient pollutant removal.

Highly selective synthesis of surface FeIV=O with nanoscale zero-valent iron and chlorite for efficient oxygen transfer reactions.

High-valent iron-oxo species (FeIV=O) has been a long-sought-after oxygen transfer reagent in biological and catalytic chemistry but suffers from a giant challenge in its gentle and selective synthesis. Herein, we propose a new strategy to synthesize surface FeIV=O (≡FeIV=O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO2-) as the oxidant, which possesses an impressive ≡FeIV=O selectivity of 99%. ≡FeIV=O can be energetically formed from the ferrous (FeII) sites on nZVI through heterolytic Cl-O bond dissociation of ClO2- via a synergistic effect between electron-donating surface ≡FeII and proximal electron-withdrawing H2O, where H2O serves as a hydrogen-bond donor to the terminal O atom of the adsorbed ClO2- thereby prompting the polarization and cleavage of Cl-O bond for the oxidation of ≡FeII toward the final formation of ≡FeIV=O. With methyl phenyl sulfoxide (PMS16O) as the probe molecule, the isotopic labeling experiment manifests an exclusive 18O transfer from Cl18O2- to PMS16O18O mediated by ≡FeIV=18O. We then showcase the versatility of ≡FeIV=O as the oxygen transfer reagent in activating the C-H bond of methane for methanol production and facilitating selective triphenylphosphine oxide synthesis with triphenylphosphine. We believe that this new ≡FeIV=O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value-added chemical synthesis.

VSIG4 Silencing Inhibits Glioblastoma Growth by Regulating the JAK2/STAT3 Pathway.

Background: Glioblastoma (GBM) is the most common malignant primary brain tumour in adults. VSIG4 has been identified to be associated with GBM. We aimed to determine the downstream regulatory mechanisms of VSIG4 in GBM. Methods: Differential expression of VSIG4 was analysed using GEPIA. The expression of VSIG4 was assessed by RT-qPCR and its downstream genes were screened by transcriptome sequencing. The expression of pyroptosis-related proteins and the JAK2/STAT3 pathway was measured by Western blotting. GBM cell viability, migration, and invasion were detected using CCK-8, scratch, and Transwell assays. The levels of pyroptosis-related factors were measured using ELISA. The effect of VSIG4 on GBM tumour growth in vivo was explored by constructing a xenograft tumour model. Results: VSIG4 expression was upregulated in GBM. Functionally, silencing of VSIG4 inhibited proliferation, invasion, and migration of U251 and LN229 cells, and promoted pyroptosis. Mechanically, transcriptome sequencing revealed that the JAK2/STAT3 pathway might be a downstream regulator of VSIG4. Further studies proved that silencing of VSIG4 enhanced the expression of p-JAK2 and p-STAT3, and the JAK2/STAT3 pathway inhibitor relieved the suppression of VSIG4 silencing on GBM cell viability, invasion, and migration. Furthermore, in vivo experiments further validated that knockdown of VSIG4 inhibited the growth of GBM tumors. Conclusion: In GBM, silencing VSIG4 promoted pyroptosis and inhibited tumor progression by regulating the JAK2/STAT3 signaling pathway.

Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation.

Stable metal nitrides (MN) are promising materials to fit the future "green" ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

Solar Hydrocarbons: Single-Step, Atmospheric-Pressure Synthesis of C2 -C4 Alkanes and Alkenes from CO2.

Cobalt ferrite (CoFe2 O4 ) spinel has been found to produce C2 -C4 hydrocarbons in a single-step, ambient-pressure, photocatalytic hydrogenation of CO2 with a rate of 1.1 mmol g-1 h-1 , selectivity of 29.8 % and conversion yield of 12.9 %. On stream the CoFe2 O4 reconstructs to a CoFe-CoFe2 O4 alloy-spinel nanocomposite which facilitates the light-assisted transformation of CO2 to CO and hydrogenation of the CO to C2 -C4 hydrocarbons. Promising results obtained from a laboratory demonstrator bode well for the development of a solar hydrocarbon pilot refinery.

Visible Light-Driven Conversion of Carbon-Sequestrated Seawater into Stoichiometric CO and HClO with Nitrogen-Doped BiOCl Atomic Layers.

Seawater is one of the most important CO2 sequestration media for delivering value-added chemicals/fuels and active chlorine; however, this scenario is plagued by sluggish reaction rates and poor product selectivity. Herein, we first report the synthesis of nitrogen-doped BiOCl atomic layers to directly split carbon-sequestrated natural seawater (Yellow Sea, China) into stoichiometric CO (92.8 µmol h-1 ) and HClO (83.2 µmol h-1 ) under visible light with selectivities greater than 90 %. Photoelectrons enriched on the exposed BiOCl{001} facet kinetically facilitate CO2 -to-CO reduction via surface-doped nitrogen bearing Lewis basicity. Photoholes, mainly located on the lateral facets of van der Waals gaps, promote the selective oxidation of Cl- into HClO. Sequestrated CO2 also maintains the pH of seawater at around 4.2 to prevent the alkaline earth cations from precipitating. The produced HClO can effectively kill typical bacteria in the ballast water of ocean-going cargo ships, offering a green and safe way for onsite sterilization.

ZnO Nanorod-Immobilized Pt Single-Atoms as an Ultrasensitive Sensor for Triethylamine Detection.

Triethylamine (TEA) is a flammable and highly toxic gas, and the fast, accurate, and sensitive detection of gas TEA remains greatly challenging. Herein, we report a ZnO nanorod anchored with a single-atom Pt catalyst (Pt1/ZnO) as a gas sensor for TEA detection. The sensor shows high selectivity and high response to gas TEA with a response value of 4170 at 200 °C, which is 92 times higher than that of pure ZnO. Moreover, the Pt1/ZnO sensor has very short response and recovery times of only 34 and 76 s, respectively, and also has a high response to ppb-level TEA gas (100 ppb-21.6). The gas-sensing enhancement mechanism of the Pt1/ZnO sensor to gas TEA was systematically investigated using band structure analysis, in situ diffuse reflectance infrared Fourier transformation spectroscopy, and density functional theory calculations. The results show that the oxygen vacancies on Pt1/ZnO can effectively activate the adsorbed oxygen. Moreover, chemical bonds can be formed between Pt single atoms and N atoms in TEA to achieve effective adsorption and activation of TEA molecules, facilitating the reaction between TEA and the adsorbed oxygen on Pt1/ZnO, and thereby obtaining high gas-sensing performance. This work highlights the crucial role of Pt single-atom in improving the sensing performance for gas TEA detection, paving the way for developing more advanced gas sensors.

The Efficacy and Safety of Intraoperative Radiotherapy in the Treatment of Recurrent High-Grade Glioma: A Single-Center Prospective Study.

BACKGROUND: High-grade gliomas are treated following a standard protocol; however, tumor recurrence is almost inevitable. Recurrent high-grade gliomas have an extremely poor prognosis, and there are no clear treatment guidelines. In this stud, we evaluated the safety and effectiveness of intraoperative radiotherapy (IORT) for recurrent high-grade glioma. METHODS: In this prospective randomized study begun in April 2018, patients ≥18 years of age with a Karnofsky Performance Status >50 and recurrent high-grade glioma were randomly assigned in a 1:1 ratio to tumor resection and IORT or tumor resection alone. RESULTS: Twenty-two patients were allocated to the IORT group and 21 to receive surgery only (operation group). Clinical data of 42 enrolled patients were involved in the analysis. The progression-free survival of the IORT group was 9.6 months and of the operation group was 7.3 months (P = 0.018), and the overall survival of the 2 groups was 13.5 months and 10.2 months, respectively (P = 0.054). Univariate and multivariate analysis indicated that preoperative Karnofsky Performance Status >70 and IORT were protective factors for patients with recurrent high-grade glioma. A patient who underwent conventional fractionated radiotherapy within 6 months of receiving IORT died on the ninth day after undergoing tumor resection and IORT because of severe cerebral edema. The total operation time was longer in the IORT group, but there were no differences in intraoperative bleeding or adverse events between the 2 groups. CONCLUSIONS: IORT with low-energy radiography at a dose of 30-40 Gy is generally safe and effective for patients with recurrent glioma. However, IORT should not be performed for patients who have received conventional fractionated radiotherapy within 6 months.

Engineered disorder in CO2 photocatalysis.

Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO2 can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO2 forms a core-shell c-TiO2@a-TiO2-x(OH)y heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity. Specifically, these SFLPs heterolytically dissociate dihydrogen at room temperature to form charge-balancing protonated hydroxyl groups and hydrides at unsaturated titanium surface sites, which display high reactivity towards CO2 reduction. This crystalline-amorphous heterostructure also boosts light absorption, charge carrier separation and transfer to SFLPs, while prolonged carrier lifetimes and photothermal heat generation further enhance reactivity. The collective results of this study motivate a general approach for catalytically generating sustainable chemicals and fuels through engineered disorder in heterogeneous CO2 photocatalysts.

New black indium oxide-tandem photothermal CO2-H2 methanol selective catalyst.

It has long been known that the thermal catalyst Cu/ZnO/Al2O3(CZA) can enable remarkable catalytic performance towards CO2 hydrogenation for the reverse water-gas shift (RWGS) and methanol synthesis reactions. However, owing to the direct competition between these reactions, high pressure and high hydrogen concentration (≥75%) are required to shift the thermodynamic equilibrium towards methanol synthesis. Herein, a new black indium oxide with photothermal catalytic activity is successfully prepared, and it facilitates a tandem synthesis of methanol at a low hydrogen concentration (50%) and ambient pressure by directly using by-product CO as feedstock. The methanol selectivities achieve 33.24% and 49.23% at low and high hydrogen concentrations, respectively.

Oxygen and Chlorine Dual Vacancies Enable Photocatalytic O2 Dissociation into Monatomic Reactive Oxygen on BiOCl for Refractory Aromatic Pollutant Removal.

Room-temperature molecular oxygen (O2) dissociation is challenging toward chemical reactions due to its triplet ground-state and spin-forbidden characteristic. Herein, we demonstrate that BiOCl of oxygen and chlorine dual vacancies can photocatalytically dissociate O2 into monatomic reactive oxygen (•O-) for the ring opening of aromatic refractory pollutants toward deep oxidation. The electron-rich and geometry-flexible dual vacancies of oxygen and chlorine remarkably lengthen the O-O bond of adsorbed O2 from 1.21 to 2.74 Å, resulting in the rapid O2 dissociation and the subsequent •O- formation. During the photocatalytic degradation of sulfamethazine, the in situ-formed •O- plays an indispensable role in breaking the critical intermediate of pyrimidine containing a stubborn aromatic heterocyclic ring, thus facilitating the overall mineralization. More importantly, BiOCl of oxygen and chlorine dual vacancies is also superior to its monovacancy counterparts on the degradation of other refractory pollutants containing conjugated six-membered rings, including p-chlorophenol, p-chloronitrobenzene, p-hydroxybenzoic acid, and p-nitrobenzoic acid. This study sheds light on the importance of sophisticated defects for regulating the O2 activation manner and deliveries a novel O2 activation approach for environmental remediation with solar energy.

Solar Urea: Towards a Sustainable Fertilizer Industry.

Urea, an agricultural fertilizer, nourishes humanity. The century-old Bosch-Meiser process provides the world's urea. It is multi-step, consumes enormous amounts of non-renewable energy, and has a large CO2 footprint. Thus, developing an eco-friendly synthesis for urea is a priority. Herein we report a single-step Pd/LTA-3A catalyzed synthesis of urea from CO2 and NH3 under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH3 and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H2 O to shift the equilibrium towards urea production. The solar urea conversion rate from NH3 and CO2 is 87 µmol g-1 h-1 . This advance represents a first step towards the use of solar energy in urea production. It provides insights into green fertilizer production, and inspires the vision of sustainable, modular plants for distributed production of urea on farms.

In Situ Visualization on Surface Oxidative Corrosion with Free Radicals: Black Phosphorus Nanoflake as an Example.

Free radicals exert a significant impact on the fate of redox-active substances and play a crucial role in the surface corrosion of solid in environment. Dynamic visualization on the response of the surface to the free radicals at nanoscale is essential to explore the mechanism. Environmental transmission electron microscopy will be a powerful tool for dynamic changes of the interface redox process of solid surface with electron beams induced free radicals, to simulate the redox process of a solid in the environment. Black phosphorus (BP), an environment-sensitive material, is selected as an example to visualize the degradation pathways with environmental transmission electron microscopy. The distribution of the corrosion initiation points, formation and growth of corrosion areas, and the eventual splintering and disappearance of BP nanoflakes are recorded vividly. In situ results are substantiated by the ex situ experiments and density functional theory (DFT) calculations. Results show that degradation originates at the edges and defect structures when the humidity reaches high enough. The microscopic structural oxidative etching of solid surface with radicals in natural light is simulated with radicals produced by electron beam irradiation on suspending medium O2 and H2O for the first time. This method will offer unprecedented details and valuable insights into the mechanism involved in the oxidative etching with natural light.

Near-Perfect Absorbing Copper Metamaterial for Solar Fuel Generation.

Metamaterials are a new class of artificial materials that can achieve electromagnetic properties that do not occur naturally, and as such they can also be a new class of photocatalytic structures. We show that metal-based catalysts can achieve electromagnetic field amplification and broadband absorption by decoupling optical properties from the material composition as exemplified with a ZnO/Cu metamaterial surface comprising periodically arranged nanocubes. Through refractive index engineering close to the index of air, the metamaterial exhibits near-perfect 98% absorption. The combination of plasmonics and broadband absorption elevates the weak electric field intensities across the nonplasmonic absorption range. This feedback between optical excitation and plasmonic excitation dramatically enhances light-to-dark catalytic rates by up to a factor of 181 times, compared to a 3 times photoenhancement of ZnO/Cu nanoparticles or films, and with angular invariance. These results show that metamaterial catalysts can act as a singular light harvesting device that substantially enhances photocatalysis of important reactions.

Van Der Waals gap-rich BiOCl atomic layers realizing efficient, pure-water CO2-to-CO photocatalysis.

Photocatalytic CO2 reduction (PCR) is able to convert solar energy into chemicals, fuels, and feedstocks, but limited by the deficiencies of photocatalysts in steering photon-to-electron conversion and activating CO2, especially in pure water. Here we report an efficient, pure water CO2-to-CO conversion photocatalyzed by sub-3-nm-thick BiOCl nanosheets with van der Waals gaps (VDWGs) on the two-dimensional facets, a graphene-analog motif distinct from the majority of previously reported nanosheets usually bearing VDWGs on the lateral facets. Compared with bulk BiOCl, the VDWGs-rich atomic layers possess a weaker excitonic confinement power to decrease exciton binding energy from 137 to 36 meV, consequently yielding a 50-fold enhancement in the bulk charge separation efficiency. Moreover, the VDWGs facilitate the formation of VDWG-Bi-VO••-Bi defect, a highly active site to accelerate the CO2-to-CO transformation via the synchronous optimization of CO2 activation, *COOH splitting, and *CO desorption. The improvements in both exciton-to-electron and CO2-to-CO conversions result in a visible light PCR rate of 188.2 µmol g-1 h-1 in pure water without any co-catalysts, hole scavengers, or organic solvents. These results suggest that increasing VDWG exposure is a way for designing high-performance solar-fuel generation systems.

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO2 Photoreduction.

The objective of photocatalytic CO2 reduction (PCR) is to achieve high selectivity for a single energy-bearing product with high efficiency and stability. The bulk configuration usually determines charge carrier kinetics, whereas surface atomic arrangement defines the PCR thermodynamic pathway. Concurrent engineering of bulk and surface structures is therefore crucial for achieving the goal of PCR. Herein, an ultrastable and highly selective PCR using homogeneously doped BiOCl nanosheets synthesized via an inventive molten strategy is presented. With B2 O3 as both the molten salt and doping precursor, this new doping approach ensures boron (B) doping from the surface into the bulk with dual functionalities. Bulk B doping mitigates strong excitonic effects confined in 2D BiOCl by significantly reducing exciton binding energies, whereas surface-doped B atoms reconstruct the BiOCl surface by extracting lattice hydroxyl groups, resulting in intimate B-oxygen vacancy (B-OV) associates. These exclusive B-OV associates enable spontaneous CO2 activation, suppress competitive hydrogen evolution and promote the proton-coupled electron transfer step by stabilizing *COOH for selective CO generation. As a result, the homogeneous B-doped BiOCl nanosheets exhibit 98% selectivity for CO2 -to-CO reduction under visible light, with an impressive rate of 83.64 µmol g-1 h-1 and ultrastability for long-term testing of 120 h.

Kirkendall Effect Boosts Phosphorylated nZVI for Efficient Heavy Metal Wastewater Treatment.

Removal of non-biodegradable heavy metals has been the top priority in wastewater treatment and the development of green technologies remains a significant challenge. We demonstrate that phosphorylated nanoscale zero-valent iron (nZVI) is promising for removal of heavy metals (NiII , CuII , CrVI , HgII ) via a boosted Kirkendall effect. Phosphorylation confines tensile hoop stress on the nZVI particles and "breaks" the structurally dense spherical nZVI to produce numerous radial nanocracks. Exemplified by NiII removal, the radial nanocracks favor the facile inward diffusion of NiII and the rapid outward transport of electrons and ferrous ions through the oxide shell for surface (NiII /electron) and boundary (NiII /Fe0 ) galvanic exchange. Accompanied by a pronounced hollowing phenomenon, phosphorylated nZVI can instantly reduce and immobilize NiII throughout the oxide shell with a high capacity (258 mg Ni g-1 Fe). For real electroplating factory wastewater treatment, this novel nZVI performs simultaneous NiII and CuII removal, producing effluent of stable quality that meets local discharge regulations.