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Background: The extra-articular lesions of rheumatoid arthritis (RA) are reported to involve multiple organs and systems throughout the body, including the heart, kidneys, liver, and lungs. This study assessed the potential causal relationship between RA and the risk of chronic kidney diseases (CKDs) using the Mendelian randomization (MR) analysis., Method: Independent genetic instruments related to RA and CKD or CKD subtypes at the genome-wide significant level were chosen from the publicly shared summary-level data of genome-wide association studies (GWAS). Then, we obtained some single-nucleotide polymorphisms (SNPs) as instrumental variables (IVs), which are associated with RA in individuals of European origin, and had genome-wide statistical significance (p5 × 10 -8 ). The inverse-variance weighted (IVW) method was the main analysis method in MR analysis. The other methods, such as weighted median, MR-Egger, simple mode, and weighted mode were used as supplementary sensitivity analyses. Furthermore, the levels of pleiotropy and heterogeneity were assessed using Cochran's Q test and leave-one-out analysis. Furthermore, the relevant datasets were obtained from the Open GWAS database., Results: Using the IVW method, the main method in MR analysis, the results showed that genetically determined RA was associated with higher risks of CKD [odds ratio (OR): 1.22, 95% confidence interval (CI) 1.13-1.31; p  < 0.001], glomerulonephritis (OR: 1.23, 95% CI 1.15-1.31; p < 0.000), amyloidosis (OR = 1.43, 95% CI 1.10-1.88, p  < 0.001), and renal failure (OR = 1.18, 95% CI 1.00-1.38, p  < 0.001). Then, using multiple MR methods, it was confirmed that the associations persisted in sensitivity analyses, and no pleiotropy was detected., Conclusion: The findings revealed a causal relationship between RA and CKD, including glomerulonephritis, amyloidosis, and renal failure. Therefore, RA patients should pay more attention to monitoring their kidney function, thus providing the opportunity for earlier intervention and lower the risk of progression to CKDs., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Jiang, Chen, Liu, Qi, Wang, Li, Jiang, Zhang, Huang, Mao and Ying.)

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-C 3 N 4 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., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

BiOCl photocatalysis shows great promise for molecular oxygen activation and NO oxidation, but its selective transformation of NO to immobilized nitrate without toxic NO 2 emission is still a great challenge, because of uncontrollable reaction intermediates and pathways. In this study, we demonstrate that the introduction of triangle Cl-Ag 1 -Cl sites on a Cl-terminated, (001) facet-exposed BiOCl can selectively promote one-electron activation of reactant molecular oxygen to intermediate superoxide radicals (⋅O 2 - ), and also shift the adsorption configuration of product NO 3 - from the weak monodentate binding mode to a strong bidentate mode to avoid unfavorable photolysis. By simultaneously tuning intermediates and products, the Cl-Ag 1 -Cl-landen BiOCl achieved >90 % NO conversion to favorable NO 3 - of high selectivity (>97 %) in 10 min under visible light, with the undesired NO 2 concentration below 20 ppb. Both the activity and the selectivity of Cl-Ag 1 -Cl sites surpass those of BiOCl surface sites (38 % NO conversion, 67 % NO 3 - selectivity) or control O-Ag 1 -O sites on a benchmark photocatalyst P25 (67 % NO conversion and 87 % NO 3 - 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., (© 2023 Wiley-VCH GmbH.)

Crafting vacancies offers an efficient route to upgrade the selectivity and productivity of nanomaterials for CO 2 electroreduction. However, defective nanoelectrocatalysts bear catalytically active vacancies mostly on their surface, with the rest of the interior atoms adiaphorous for CO 2 -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&#95;d orbital with the C&#95;P orbital of the *COOH intermediate, leading to an accelerated CO 2 -to-CO transformation. These structural and electronic merits allow a large-area (9 cm -2 ) electrode to generate nearly pure CO with a CO/H 2 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 CO 2 reduction.

High-valent iron-oxo species (Fe IV =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 Fe IV =O (≡Fe IV =O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO 2 - ) as the oxidant, which possesses an impressive ≡Fe IV =O selectivity of 99%. ≡Fe IV =O can be energetically formed from the ferrous (Fe II ) sites on nZVI through heterolytic Cl-O bond dissociation of ClO 2 - via a synergistic effect between electron-donating surface ≡Fe II and proximal electron-withdrawing H 2 O, where H 2 O serves as a hydrogen-bond donor to the terminal O atom of the adsorbed ClO 2 - thereby prompting the polarization and cleavage of Cl-O bond for the oxidation of ≡Fe II toward the final formation of ≡Fe IV =O. With methyl phenyl sulfoxide (PMS 16 O) as the probe molecule, the isotopic labeling experiment manifests an exclusive 18 O transfer from Cl 18 O 2 - to PMS 16 O 18 O mediated by ≡Fe IV = 18 O. We then showcase the versatility of ≡Fe IV =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 ≡Fe IV =O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value-added chemical synthesis.

Cobalt ferrite (CoFe 2 O 4 ) spinel has been found to produce C 2 -C 4 hydrocarbons in a single-step, ambient-pressure, photocatalytic hydrogenation of CO 2 with a rate of 1.1 mmol g -1  h -1 , selectivity of 29.8 % and conversion yield of 12.9 %. On stream the CoFe 2 O 4 reconstructs to a CoFe-CoFe 2 O 4 alloy-spinel nanocomposite which facilitates the light-assisted transformation of CO 2 to CO and hydrogenation of the CO to C 2 -C 4 hydrocarbons. Promising results obtained from a laboratory demonstrator bode well for the development of a solar hydrocarbon pilot refinery., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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 MN 1- x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH 1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH 1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt 1 -Pt n ) under N 2 -H 2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt 1 -Pt n 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 N 2 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.

Seawater is one of the most important CO 2 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 CO 2 -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 CO 2 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., (© 2023 Wiley-VCH GmbH.)

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., Competing Interests: The authors declare that they have no competing interests., (© 2023 Zheng et al.)

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 (Pt 1 /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 Pt 1 /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 Pt 1 /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 Pt 1 /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 Pt 1 /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.

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., (Copyright © 2023 Elsevier Inc. All rights reserved.)

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 TiO 2 can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO 2 forms a core-shell c-TiO 2 @a-TiO 2-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 CO 2 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 CO 2 photocatalysts., (© 2022. The Author(s).)

It has long been known that the thermal catalyst Cu/ZnO/Al 2 O 3 (CZA) can enable remarkable catalytic performance towards CO 2 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., (© 2022. The Author(s).)

Room-temperature molecular oxygen (O 2 ) 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 O 2 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 O 2 from 1.21 to 2.74 Å, resulting in the rapid O 2 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 O 2 activation manner and deliveries a novel O 2 activation approach for environmental remediation with solar energy.

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 O 2 and H 2 O for the first time. This method will offer unprecedented details and valuable insights into the mechanism involved in the oxidative etching with natural light.

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 CO 2 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 CO 2 and NH 3 under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH 3 and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H 2 O to shift the equilibrium towards urea production. The solar urea conversion rate from NH 3 and CO 2 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., (© 2021 Wiley-VCH GmbH.)

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.

Photocatalytic CO 2 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 CO 2 , especially in pure water. Here we report an efficient, pure water CO 2 -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-V O •• -Bi defect, a highly active site to accelerate the CO 2 -to-CO transformation via the synchronous optimization of CO 2 activation, *COOH splitting, and *CO desorption. The improvements in both exciton-to-electron and CO 2 -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., (© 2021. The Author(s).)

The objective of photocatalytic CO 2 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 B 2 O 3 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 CO 2 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 CO 2 -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., (© 2021 Wiley-VCH GmbH.)

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 (Ni II , Cu II , Cr VI , Hg II ) 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 Ni II removal, the radial nanocracks favor the facile inward diffusion of Ni II and the rapid outward transport of electrons and ferrous ions through the oxide shell for surface (Ni II /electron) and boundary (Ni II /Fe 0 ) galvanic exchange. Accompanied by a pronounced hollowing phenomenon, phosphorylated nZVI can instantly reduce and immobilize Ni II 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 Ni II and Cu II removal, producing effluent of stable quality that meets local discharge regulations., (© 2021 Wiley-VCH GmbH.)

Herein is developed a ternary heterostructured catalyst, based on a periodic array of 1D TiN nanotubes, with a TiO 2 nanoparticulate intermediate layer and a In 2 O 3- x (OH) y nanoparticulate shell for improved performance in the photocatalytic reverse water gas shift reaction. It is demonstrated that the ordering of the three components in the heterostructure sensitively determine its activity in CO 2 photocatalysis. Specifically, TiN nanotubes not only provide a photothermal driving force for the photocatalytic reaction, owing to their strong optical absorption properties, but they also serve as a crucial scaffold for minimizing the required quantity of In 2 O 3- x (OH) y nanoparticles, leading to an enhanced CO production rate. Simultaneously, the TiO 2 nanoparticle layer supplies photogenerated electrons and holes that are transferred to active sites on In 2 O 3- x (OH) y nanoparticles and participate in the reactions occurring at the catalyst surface.

Nanoscale titanium nitride TiN is a metallic material that can effectively harvest sunlight over a broad spectral range and produce high local temperatures via the photothermal effect. Nanoscale indium oxide-hydroxide, In 2 O 3- x (OH) y , is a semiconducting material capable of photocatalyzing the hydrogenation of gaseous CO 2 ; however, its wide electronic bandgap limits its absorption of photons to the ultraviolet region of the solar spectrum. Herein, the benefits of both nanomaterials in a ternary heterostructure: TiN@TiO 2 @In 2 O 3- x (OH) y are combined. This heterostructured material synergistically couples the metallic TiN and semiconducting In 2 O 3- x (OH) y phases via an interfacial semiconducting TiO 2 layer, allowing it to drive the light-assisted reverse water gas shift reaction at a conversion rate greatly surpassing that of its individual components or any binary combinations thereof., (© 2020 Wiley-VCH GmbH.)

Optimizing kinetic barriers of ammonia synthesis to reduce the energy intensity has recently attracted significant research interest. The motivation for the research is to discover means by which activation barriers of N 2 dissociation and NH z ( z = 1-2, surface intermediates) destabilization can be reduced simultaneously, that is, breaking the "scaling relationship". However, by far only a single success has been reported in 2016 based on the discovery of a strong-weak N-bonding pair: transition metals (nitrides)-LiH. Described herein is a second example that is counterintuitively founded upon a strong-strong N-bonding pair unveiled in a bifunctional nanoscale catalyst TiO 2- x H y /Fe (where 0.02 ≤ x ≤ 0.03 and 0 < y < 0.03), in which hydrogen spillover (H) from Fe to cascade oxygen vacancies (O V -O V ) results in the trapped form of O V -H on the TiO 2- x H y component. The Fe component thus enables facile activation of N 2 , while the O V -H in TiO 2- x H y hydrogenates the N or NH z to NH 3 easily.

Herein, sulfur vacancies in magnetic greigite (SVs-Fe 3 S 4 ) nanosheets were synthesized by a one-step solvothermal method by adjusting the ethylene glycol: water ratio. Electron paramagnetic resonance spectroscopy (EPR) and X-ray photoelectron spectroscopy (XPS) revealed that SV-rich Fe 3 S 4 and SV-poor Fe 3 S 4 were acquired using 100% ethylene glycol and 100% water as solvent, respectively. A peroxidase-like activity assay demonstrated that maximum reaction rates for H 2 O 2 -mediated oxidation of 3,3',5,5'-tetramethyl-benzidine (TMB) catalyzed by the SV-rich Fe 3 S 4 was 2.3 times higher than SV-poor Fe 3 S 4 . Density functional theory (DFT) calculations and reactive oxygen species (ROS) detection confirmed that the enhanced peroxidase-like activity by SV-rich Fe 3 S 4 was attributed to efficient adsorption of H 2 O 2 and subsequent decomposition to hydroxyl radicals (•OH) on the SVs sites of Fe 3 S 4 . The SV-rich Fe 3 S 4 nanozyme was employed to develop a simple, highly sensitive and selective assay for glucose detection with a linear range of 0.5-150 μM and a detection limit of 0.1 μM (S/N = 3). A smartphone application (App) was designed and applied to efficiently detect serum glucose with the integrated analytical system based on the SV-rich Fe 3 S 4 . These new findings highlight the important role of surface defects in nanozymes on generating peroxidase-like activity for glucose detection in point-of-care diagnosis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The limitations of the Haber-Bosch reaction, particularly high-temperature operation, have ignited new interests in low-temperature ammonia-synthesis scenarios. Ambient N 2 electroreduction is a compelling alternative but is impeded by a low ammonia production rate (mostly <10 mmol g cat -1 h -1 ), a small partial current density (<1 mA cm -2 ), and a high-selectivity hydrogen-evolving side reaction. Herein, we report that room-temperature nitrate electroreduction catalyzed by strained ruthenium nanoclusters generates ammonia at a higher rate (5.56 mol g cat -1 h -1 ) than the Haber-Bosch process. The primary contributor to such performance is hydrogen radicals, which are generated by suppressing hydrogen-hydrogen dimerization during water splitting enabled by the tensile lattice strains. The radicals expedite nitrate-to-ammonia conversion by hydrogenating intermediates of the rate-limiting steps at lower kinetic barriers. The strained nanostructures can maintain nearly 100% ammonia-evolving selectivity at >120 mA cm -2 current densities for 100 h due to the robust subsurface Ru-O coordination. These findings highlight the potential of nitrate electroreduction in real-world, low-temperature ammonia synthesis.

Introduction: microRNAs (miRs) have been reported as blood-based noninvasive indicators for the diagnosis of various diseases. However, the utility of whole blood-based miRs in the diagnosis of intracranial aneurysm (IA) is still not clear. The present study aimed to examine miR expression profiling in the peripheral whole blood of IA patients and healthy controls., Material and Methods: Seventy-three IA patients, including 34 unruptured and 39 ruptured, and 28 healthy subjects, were recruited for diagnostic analysis. microRNA (miR) expression profiling in whole blood from healthy controls and IA patients was evaluated using miRNA microarray assay. RT-qPCR was used to evaluate miR expression. Receiver operating characteristics (ROC) curves and the area under the ROC curves (AUC) were used to calculate the diagnostic power of miRs in whole blood of IA., Results: We observed significantly higher miR-21 and miR-92 expression levels in aneurysmal tissues and whole blood of IA patients as compared to healthy subjects. miR-21 expression level was significantly positively correlated with miR-92 in IA tissues and whole blood of IA patients. ROC analysis revealed that miR-21 (AUC = 0.843, sensitivity = 0.849, specificity = 0.750) and miR-92 (AUC = 0.892, sensitivity = 0.945, specificity = 0.786) were promising in diagnosis of IA with high detectability. Intriguingly, miR-21 combined with miR-92 markedly improved the diagnostic power of IA (AUC = 0.920, sensitivity = 1.000, specificity = 0.786)., Conclusions: miR-21 combined with miR-92 could be considered as a potential biomarker for IA screening., Competing Interests: The authors declare no conflict of interest., (Copyright: © 2020 Termedia & Banach.)

Background: Relapse of primary central nervous system (CNS) lymphoma (PCNSL) occurs primarily at the initial site. Relapse outside the CNS is rare., Case Description: We present the case of a 62-year-old immunocompetent man who underwent a stereotactic biopsy to diagnose PCNSL and subsequent placement of ventriculoperitoneal shunt (VPS) for symptom relief in November 2012. He got complete remission after 6 cycles of high-dose methotrexate-based chemotherapy. In August 2017, relapse of lymphoma occurred in the abdomen, left basal ganglia, and bilateral ventricle with the largest lesion being around the VPS in the abdomen. He got complete remission after 6 cycles of R-CHOP (rituximab, cyclophosphamide, epirubicin, vincristine and prednisolone) plus 8 cycles of high-dose methotrexate chemotherapy., Conclusions: Here we report the first case of extra-CNS relapse of PCNSL around the site of VPS in the abdomen after intensive chemotherapy. Neurosurgeons should be aware of a potential risk of PCNSL spread along the VPS., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Semiconductor photocatalytic technology has great potential for the removal of dilute gaseous NO in indoor and outdoor atmospheres but suffers from unsatisfactory NO-removal selectivity due to undesirable NO 2 byproduct generation. In this study, we demonstrate that the 99% selectivity of photocatalytic NO oxidation toward nitrate can be achieved over blue TiO 2 bearing oxygen vacancies (OVs) under visible-light irradiation. First-principles density functional theory calculation and experimental results suggested that the OVs of blue TiO 2 with localized electrons could facilitate the molecular oxygen activation through single-electron pathways to generate ·O 2 - and simultaneously promote the photogenerated hole annihilation. The generated ·O 2 - directly converted NO to nitrate, while the hole annihilation inhibited the side-reaction between holes and NO to avoid toxic NO 2 byproduct formation, resulting in the highly selective removal of NO. This study reveals the dual functions of OVs in defective photocatalysts and also provides fundamental guidance for the selective purification of NO with photocatalytic technology.

Background: Primary central nervous system lymphoma (PCNSL) is a rare disease affecting the brain, leptomeninges, spinal cord, cerebrospinal fluid, or vitreoretinal compartment, without evidence of systemic disease. Prognosis is still poor after intensive methotrexate-based chemotherapy., Methods: Clinical data of 91 patients treated in a tertiary referral center during a 13-year period were retrospectively reviewed., Results: The estimated median progression-free survival and overall survival (OS) for the entire cohort were 39.1 months (95% confidence interval [CI], 14.1-64.0 months) and 54.5 months (95% CI, 28.9-80.1 months), respectively. Estimated 5-year progression-free survival and OS were 37.0% ± 6.5% and 47.5% ± 7.5%. Survival was associated with cycles of methotrexate only in multivariate analysis. Seventy-four patients received methotrexate-based chemotherapy after diagnosis. Thirty-nine patients experienced disease progression. Patients with relapsed/refractory disease had a poor survival, with median second OS (calculated from the date of first disease progression to the time of death from any cause) being 7.2 months (95% CI, 2.5-12.00 months). Three patients responded to ibrutinib after disease progression and incurred no fungal infection., Conclusions: The outcomes of patients with PCNSL treated in our cohort are still poor. Relapse or refractory PCNSL and those not tolerating aggressive chemotherapy urgently require new approaches to improve their still dismal prognosis. Novel agents such as ibrutinib have shown promising clinical activity. Future studies should focus on the predictive biomarkers for the treatment of PCNSL with novel agents to provide precision medicine for PCNSL., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Catalytic ammonia synthesis from dinitrogen (N2) under mild conditions has been considered to be the "holy grail" of N2 fixation, which is one of the most important chemical processes in the agriculture, biological and industrial fields. Given that current artificial N2 fixation is still dominated by the energy-intensive Haber-Bosch process, solar N2 fixation represents an encouraging and fascinating route for carbon-free and energy-saving N2 fixation. However, its practical application is seriously hampered by surface sluggish reaction kinetics. In this minireview, we share our perspectives on the use of two-dimensional (2D) nanosheets for the manipulation of photocatalytic N2 fixation. Nanosheet photocatalysts serve as the perfect platform for the engineering of surface active sites, including defects and iron, all of which can not only bolster photon-exciton interaction toward robust charge carriers generation upon light absorption, but also mimic the function schemes of MoFe-cofactor in nitrogenase toward sufficient N2 binding and activation. These merits endowed by nanosheets photocatalysts provide instructive information on exploring the rich nitrogen photochemistry on solid surfaces and offer new opportunities for the design of novel photocatalysts towards efficient N2 fixation.

Semiconductor nanowires that have been extensively studied are typically in a crystalline phase. Much less studied are amorphous semiconductor nanowires due to the difficulty for their synthesis, despite a set of characteristics desirable for photoelectric devices, such as higher surface area, higher surface activity, and higher light harvesting. In this work of combined experiment and computation, taking Zn2GeO4 (ZGO) as an example, we propose a site-specific heteroatom substitution strategy through a solution-phase ions-alternative-deposition route to prepare amorphous/crystalline Si-incorporated ZGO nanowires with tunable band structures. The substitution of Si atoms for the Zn or Ge atoms distorts the bonding network to a different extent, leading to the formation of amorphous Zn1.7Si0.3GeO4 (ZSGO) or crystalline Zn2(GeO4)0.88(SiO4)0.12 (ZGSO) nanowires, respectively, with different bandgaps. The amorphous ZSGO nanowire arrays exhibit significantly enhanced performance in photoelectrochemical water splitting, such as higher and more stable photocurrent, and faster photoresponse and recovery, relative to crystalline ZGSO and ZGO nanowires in this work, as well as ZGO photocatalysts reported previously. The remarkable performance highlights the advantages of the ZSGO amorphous nanowires for photoelectric devices, such as higher light harvesting capability, faster charge separation, lower charge recombination, and higher surface catalytic activity.

Objective: To analyze the factors that affect oculomotor nerve function recovery time in patients receiving balloon embolization for oculomotor nerve palsy caused by traumatic carotid cavernous sinus fistula., Methods: The clinical data were collected from 87 patients undergoing balloon embolization for oculomotor nerve palsy due to traumatic carotid cavernous sinus fistula from July 2005 to July 2013 and the factors affecting oculomotor nerve function recovery time was analyzed using a self-made questionnaire., Results and Conlusion: Oculomotor nerve function recovery time ranged from 1 to 6 months (mean 33.32 ± 16.76 days) in these patients. Age, severity of preoperative oculomotor nerve paralysis, injury-to-treatment time, and number of balloon used were positively correlated with nerve function recovery time, and the flow volume of traumatic carotid cavernous sinus fistula was negatively correlated with the recovery time.