Effect of corneal cross-linking on biomechanical changes following transepithelial photorefractive keratectomy and femtosecond laser-assisted LASIK.

Purpose: To evaluate the change in corneal biomechanics in patients with postoperative ectasia risk when combining two common laser vision correction procedures (tPRK and FS-LASIK) with cross-linking (in tPRK Xtra and FS-LASIK Xtra). Methods: The study included 143 eyes of 143 myopic, astigmatic patients that were divided into non-cross-linked refractive surgery groups (non-Xtra groups, tPRK and FS-LASIK) and cross-linked groups (Xtra groups, tPRK Xtra and FS-LASIK Xtra) according to an ectasia risk scoring system. The eyes were subjected to measurements including the stress-strain index (SSI), the stiffness parameter at first applanation (SP-A1), the integrated inverse radius (IIR), the deformation amplitude at apex (DA), and the ratio of deformation amplitude between apex and 2 mm from apex (DARatio2mm). The measurements were taken preoperatively and at 1, 3, and 6 months postoperatively (pos1m, pos3m, and pos6m). Posterior demarcation line depth from the endothelium (PDLD) and from the ablation surface (DLA) were recorded at pos1m. Results: SP-A1 significantly decreased, while IIR, deformation amplitude, and DARatio2mm increased significantly postoperatively in all four groups (p < 0.01)-all denoting stiffness decreases. In the FS-LASIK group, the changes in IIR, DA, and DARatio2mm were 32.7 ± 15.1%, 12.9 ± 7.1%, and 27.2 ± 12.0% respectively, which were significantly higher (p < 0.05) compared to 20.1 ± 12.8%, 6.4 ± 8.2%, and 19.7 ± 10.4% in the FS-LASIK Xtra group. In the tPRK group, the change in IIR was 27.3 ± 15.5%, significantly larger than 16.9 ± 13.4% in the tPRK Xtra group. The changes of SSI were minimal in the tPRK (-1.5 ± 21.7%, p = 1.000), tPRK Xtra (8.4 ± 17.9%, p = 0.053), and FS-LASIK Xtra (5.6 ± 12.7%, p = 0.634) groups, but was significant in the FS-LASIK group (-12.1 ± 7.9%, p < 0.01). After correcting for baseline biomechanical metrics, preoperative bIOP and the change in central corneal thickness (△CCT) from pre to pos6m, the changes in the IIR in both FS-LASIK and tPRK groups, as well as DA, DARatio2mm and SSI in the FS-LASIK group remained statistically greater than their corresponding Xtra groups (all p < 0.05). Most importantly, after correcting for these covariates, the changes in DARatio2mm in the FS-LASIK Xtra became statistically smaller than in the tPRK Xtra (p = 0.017). Conclusion: The statistical analysis results indicate that tPRK Xtra and FS-LASIK Xtra effectively reduced the biomechanical losses caused by refractive surgery (tPRK and FS-LASIK). The decrease in corneal overall stiffness was greater in FS-LASIK than in tPRK, and the biomechanical enhancement of CXL was also higher following LASIK than after tPRK.

A Pilot Study on Bioaccumulation and Tissue Distribution of Mercury in Barn Swallow (Hirundo rustica).

Although extensive research has been carried out on the occurrence of mercury (Hg) in biota, bioaccumulation and tissue distribution of Hg in songbirds have not been well characterized. In the present study, Hg was investigated in insects and barn swallows (Hirundo rustica) to explore the bioaccumulation characteristics of Hg. Hg in swallow feathers and tissues including muscle, liver, and bone was investigated to determine the tissue distribution of Hg. The concentrations of Hg were 1.39 ± 1.01 µg/g, 0.33 ± 0.09 µg/g, 0.47 ± 0.10 µg/g, and 0.23 ± 0.09 µg/g in feather, muscle, liver, and bone samples, respectively. The trophic magnification factor of Hg in swallows and insects was higher than 1. However, the Hg concentrations in swallow feathers were not significantly correlated with stable isotope values of carbon or nitrogen, which implies the complex food sources and exposure processes of Hg for swallows. Feathers had significantly higher concentrations of Hg than liver, muscle, and bone samples (p < 0.01 for all comparisons). Feather, muscle, bone, and other organs had fractions of 64.4 ± 11.9%, 6.07 ± 2.06%, 20.0 ± 8.19%, and 9.56 ± 2.96% in total body burden of Hg in swallows. Hg in feathers contributed more than half of Hg in the whole body for most swallow individuals. Swallows may efficiently eliminate Hg by molting, and the excretion flux of Hg and other contaminants via molting deserves more investigation.

Low-Overpotential Rechargeable Na-CO2 Batteries Enabled by an Oxygen-Vacancy-Rich Cobalt Oxide Catalyst.

Rechargeable sodium-carbon dioxide (Na-CO2) batteries have been proposed as a promising CO2 utilization technique, which could realize CO2 reduction and generate electricity at the same time. They suffer, however, from several daunting problems, including sluggish CO2 reduction and evolution kinetics, large polarization, and poor cycling stability. In this study, a rambutan-like Co3O4 hollow sphere catalyst with abundant oxygen vacancies was synthesized and employed as an air cathode for Na-CO2 batteries. Density functional theory calculations reveal that the abundant oxygen vacancies on Co3O4 possess superior CO2 binding capability, accelerating CO2 electroreduction, and thereby improving the discharge capacity. In addition, the oxygen vacancies also contribute to decrease the CO2 decomposition free energy barrier, which is beneficial for reducing the overpotential further and improving round-trip efficiency. Benefiting from the excellent catalytic ability of rambutan-like Co3O4 hollow spheres with abundant oxygen vacancies, the fabricated Na-CO2 batteries exhibit extraordinary electrochemical performance with a large discharge capacity of 8371.3 mA h g-1, a small overpotential of 1.53 V at a current density of 50 mA g-1, and good cycling stability over 85 cycles. These results provide new insights into the rational design of air cathode catalysts to accelerate practical applications of rechargeable Na-CO2 batteries and potentially Na-air batteries.

Biomagnification of persistent organic pollutants (POPs) in detritivorous, phytophagous, and predatory invertebrates: How POPs enter terrestrial food web?

Invertebrates are primary contributors to fluxes of nutrients, energy, and contaminants in terrestrial food webs, but the trophodynamic of contaminants in invertebrate food chains is not fully understood. In this study, occurrence and biomagnification of persistent organic pollutants (POPs) were assessed in detritivorous, phytophagous, and predatory invertebrate food chains. Detritivorous species (earthworm and dung beetle) have higher concentrations of POPs than other species. Different composition patterns and biomagnification factors (BMFs) of POPs were observed for invertebrate species. Negative correlations were found between BMFs and log KOW of POPs for detritivorous and most phytophagous species. In contrast, parabolic relationships between BMFs and log KOW were observed in snails and predatory species, possibly attributed to the efficient digestion and absorption of diet and POPs for them. Bioenergetic characteristics are indicative of the biomagnification potential of POPs in terrestrial wildlife, as suggested by the significant and positive correlation between basal metabolic rates (BMRs) and BMFs of BDE 153 for invertebrates, amphibians, reptiles, birds, and mammals. The estimations of dietary exposure suggest that the terrestrial predators, especially feeding on the underground invertebrates, could be exposed to high level POPs from invertebrates.

2D Ferromagnetic M3 GeTe2 (M = Ni/Fe) for Boosting Intermediates Adsorption toward Faster Water Oxidation.

In this work, 2D ferromagnetic M3 GeTe2 (MGT, M = Ni/Fe) nanosheets with rich atomic Te vacancies (2D-MGTv ) are demonstrated as efficient OER electrocatalyst via a general mechanical exfoliation strategy. X-ray absorption spectra (XAS) and scanning transmission electron microscope (STEM) results validate the dominant presence of metal-O moieties and rich Te vacancies, respectively. The formed Te vacancies are active for the adsorption of OH* and O* species while the metal-O moieties promote the O* and OOH* adsorption, contributing synergistically to the faster oxygen evolution kinetics. Consequently, 2D-Ni3 GeTe2v exhibits superior OER activity with only 370 mV overpotential to reach the current density of 100 mA cm-2 and turnover frequency (TOF) value of 101.6 s-1 at the overpotential of 200 mV in alkaline media. Furthermore, a 2D-Ni3 GeTe2v -based anion-exchange membrane (AEM) water electrolysis cell (1 cm2 ) delivers a current density of 1.02 and 1.32 A cm-2 at the voltage of 3 V feeding with 0.1 and 1 m KOH solution, respectively. The demonstrated metal-O coordination with abundant atomic vacancies for ferromagnetic M3 GeTe2 and the easily extended preparation strategy would enlighten the rational design and fabrication of other ferromagnetic materials for wider electrocatalytic applications.

Targeting Magnaporthe oryzae effector MoErs1 and host papain-like protease OsRD21 interaction to combat rice blast.

Effector proteins secreted by plant pathogenic fungi are important artilleries against host immunity, but there is no precedent of such effectors being explored as antifungal targets. Here we demonstrate that MoErs1, a species-specific effector protein secreted by the rice blast fungus Magnaporthe oryzae, inhibits the function of rice papain-like cysteine protease OsRD21 involved in rice immunity. Disrupting MoErs1-OsRD21 interaction effectively controls rice blast. In addition, we show that FY21001, a structure-function-based designer compound, specifically binds to and inhibits MoErs1 function. FY21001 significantly and effectively controls rice blast in field tests. Our study revealed a novel concept of targeting pathogen-specific effector proteins to prevent and manage crop diseases.

OXCT1 regulates hippocampal neurogenesis and alleviates cognitive impairment via the Akt/GSK-3ß/ß-catenin pathway after subarachnoid hemorrhage.

BACKGROUND: Subarachnoid hemorrhage (SAH) is a life-threatening neurological disease that usually has a poor prognosis. Neurogenesis is a potential therapeutic target for brain injury. Ketone metabolism also plays neuroprotective roles in many neurological disorders. OXCT1 (3-Oxoacid CoA-Transferase 1) is the rate-limiting enzyme of ketone body oxidation. In this study, we explored whether increasing ketone oxidation by upregulating OXCT1 in neurons could promote neurogenesis after SAH, and evaluated the potential mechanism involved in this process. METHODS: The ß-hydroxybutyrate content was measured using an enzymatic colorimetric assay. Adeno-associated virus targeting neurons was injected to overexpress OXCT1, and the expression and localization of proteins were evaluated by western blotting and immunofluorescence staining. Adult hippocampal neurogenesis was evaluated by dual staining with doublecortin and 5-Ethynyl-2'-Deoxyuridine. LY294002 was intracerebroventricularly administered to inhibit Akt activity. The Morris water maze and Y-maze tests were employed to assess cognitive function after SAH. RESULTS: The results showed that OXCT1 expression and hippocampal neurogenesis significantly decreased in the early stage of SAH. Overexpression of OXCT1 successfully increased hippocampal neurogenesis via activation of Akt/GSK-3ß/ß-catenin signaling and improved cognitive function, both of which were reversed by administration of LY294002. CONCLUSIONS: OXCT1 regulated hippocampal ketone body metabolism and increased neurogenesis through mechanisms mediated by the Akt/GSK-3ß/ß-catenin pathway, improving cognitive impairment after SAH.

Electron Localization in Rationally Designed Pt1Pd Single-Atom Alloy Catalyst Enables High-Performance Li-O2 Batteries.

Li-O2 batteries (LOBs) are considered as one of the most promising energy storage devices due to their ultrahigh theoretical energy density, yet they face the critical issues of sluggish cathode redox kinetics during the discharge and charge processes. Here we report a direct synthetic strategy to fabricate a single-atom alloy catalyst in which single-atom Pt is precisely dispersed in ultrathin Pd hexagonal nanoplates (Pt1Pd). The LOB with the Pt1Pd cathode demonstrates an ultralow overpotential of 0.69 V at 0.5 A g-1 and negligible activity loss over 600 h. Density functional theory calculations show that Pt1Pd can promote the activation of the O2/Li2O2 redox couple due to the electron localization caused by the single Pt atom, thereby lowering the energy barriers for the oxygen reduction and oxygen evolution reactions. Our strategy for designing single-atom alloy cathodic catalysts can address the sluggish oxygen redox kinetics in LOBs and other energy storage/conversion devices.

Evaluation of changes in corneal biomechanics after orthokeratology using Corvis ST.

PURPOSE: To investigate the alterations in corneal biomechanical metrics induced by orthokeratology (ortho-k) using Corvis ST and to determine the factors influencing these changes. METHOD: A prospective observational study was conducted to analyze various Corvis ST parameters in 32 children with low to moderate myopia who successfully underwent ortho-k lens fitting. Corneal biomechanical measurements via Corvis ST were acquired at six distinct time points: baseline (pre) and 2 h (pos2h), 6 h (pos6h), and 10 h (pos10h) following the removal of the first overnight wear ortho-k, one week (pos1w) and one month (pos1m) subsequent to the initiation of ortho-k. RESULT: Significant differences were observed in Corvis ST Biomechanical parameters DAR2, IIR, CBI, and cCBI post ortho-k intervention. The integration of covariates (CCT, SimK, and bIOP) mitigated the differences in DAR2, IIR, and cCBI, but not in CBI. Initially, the stiffness parameter at first applanation, SP-A1, did not demonstrate significant variations, but after adjusting for covariates, noticeable differences over time were observed. The Stress-Strain Indeces, SSIv1 and SSIv2, did not manifest considerable changes over time, irrespective of the adjustment for covariates. No significant disparities were identified among different ortho-k lens brands. CONCLUSION: Corneal biomechanics remained consistent throughout the one-month period of ortho-k lens wear. The observed changes in Corvis ST parameters subsequent ortho-k are primarily attributable to alterations in corneal pachymetry and morphology, rather than actual alterations in corneal biomechanics. The stability of corneal biomechanics post ortho-k treatment suggests the safety of this approach for adolescents from a corneal biomechanics perspective.

Recent Advances in Hierarchical Porous Engineering of MOFs and Their Derived Materials for Catalytic and Battery: Methods and Application.

Hierarchical porous materials have attracted the attention of researchers due to their enormous specific surface area, maximized active site utilization efficiency, and unique structure and properties. In this context, metal-organic frameworks (MOFs) offer a unique mix of properties that make them particularly appealing as tunable porous substrates containing highly active sites. This review focuses on recent advances in the types and synthetic strategies of hierarchical porous MOFs and their derived materials. Furthermore, it highlights the relationship between the mass diffusion and transport of hierarchical porous structures and the pore size with examples and simulations, while identifying their potential and limitations. On this basis, how the synthesis conditions affect the structure and electrochemical properties of MOFs based hierarchical porous materials with different structures is discussed, highlighting the prospects and challenges for the synthetization, as well as further scientific research and practical applications. Finally, some insights into current research and future design ideas for advanced MOFs based hierarchical porous materials are presented.

Astrocyte-derived hepcidin aggravates neuronal iron accumulation after subarachnoid hemorrhage by decreasing neuronal ferroportin1.

Iron accumulation is one of the most essential pathological events after subarachnoid hemorrhage (SAH). Ferroportin1 (FPN1) is the only transmembrane protein responsible for exporting iron. Hepcidin, as the major regulator of FPN1, is responsible for its degradation. Our study investigated how the interaction between FPN1 and hepcidin contributes to iron accumulation after SAH. We found that iron accumulation aggravated after SAH, along with decreased FPN1 in neurons and increased hepcidin in astrocytes. After knocking down hepcidin in astrocytes, the neuronal FPN1 significantly elevated, thus attenuating iron accumulation. After SAH, p-Smad1/5 and Smad4 tended to translocate into the nucleus. Moreover, Smad4 combined more fragments of the promoter region of Hamp after OxyHb stimulation. By knocking down Smad1/5 or Smad4 in astrocytes, FPN1 level restored and iron overload attenuated, leading to alleviated neuronal cell death and improved neurological function. However, the protective role disappeared after recombinant hepcidin administration. Therefore, our study suggests that owing to the nuclear translocation of transcription factors p-Smad1/5 and Smad4, astrocyte-derived hepcidin increased significantly after SAH, leading to a decreased level of neuronal FPN1, aggravation of iron accumulation, and worse neurological outcome.

Performance of Corvis ST Parameters Including Updated Stress-Strain Index in Differentiating Between Normal, Forme-Fruste, Subclinical, and Clinical Keratoconic Eyes.

PURPOSE: This study seeks to evaluate the ability of the updated stress strain index (SSIv2) and other Corvis ST biomechanical parameters in distinguishing between keratoconus at different disease stages and normal eyes. DESIGN: Diagnostic accuracy analysis to distinguish disease stages. METHODS: 1084 eyes were included and divided into groups of normal (199 eyes), forme fruste keratoconus (FFKC, 194 eyes), subclinical keratoconus (SKC, 113 eyes), mild clinical keratoconus (CKC-Ⅰ, 175 eyes), moderate clinical keratoconus (CKC-Ⅱ, 204 eyes), and severe clinical keratoconus (CKC-Ⅲ, 199 eyes). Each eye was subjected to a Corvis ST examination to determine the central corneal thickness (CCT), biomechanically corrected intraocular pressure (bIOP), SSIv2 (updated stress-strain index), and other 8 Corvis parameters including the stress-strain index (SSIv1), stiffness parameter at first applanation (SP-A1), first applanation time (A1T), Ambrósio relational thickness to the horizontal profile (ARTh), integrated inverse radius (IIR), maximum deformation amplitude (DAM), ratio between deformation amplitude at the apex and at 2 mm nasal and temporal (DARatio2), and Corvis biomechanical index (CBI). The sensitivity and specificity of these parameters in diagnosing keratoconus were analyzed through receiver operating characteristic curves. RESULTS: Before and after correction for CCT and bIOP, SSIv2 and ARTh were significantly higher and IIR and CBI were significantly lower in the normal group than in the FFKC group, SKC group and the 3 CKC groups (all P < .05). There were also significant correlations between the values of SSIv2, ARTh, IIR, CBI, and the CKC severity (all P < .05). AUC of SSIv2 was significantly higher than all other Corvis parameters in distinguishing normal eyes from FFKC, followed by IIR, ARTh and CBI. CONCLUSION: Corvis ST's updated stress-strain index, SSIv2, demonstrated superior performance in differentiating between normal and keratoconic corneas, and between corneas with different keratoconus stages. Similar, but less pronounced, performance was demonstrated by the IIR, ARTh and CBI.

Seismic behavior of precast columns with unbonded prestressed tendons and energy-dissipating bars: physical and numerical investigations.

The study of the strength and failure modes of construction components has become increasingly important with the advent of industrialized construction. Recently, because of the need to promote the survivability of both structures and persons, it has encompassed failure modes associated with seismic threats. This study reports the seismic behavior of precast segmented columns designed with both unbonded prestressed tendons (UPTs) and energy-dissipating (ED) bars. A physical specimen was subjected to a quasi-static cyclic test; this permitted the evaluation of the damage mode and behavior of the energy dissipation mechanism, and permitted the establishment and verification of a fiber beam element simulation model. The model was then used to evaluate the effects of the variation of the design parameters on the behavior of precast assembled columns. The test specimen exhibited stable energy dissipation and a pinching effect during cyclic loading. An analysis using the fiber beam element model with varying design parameters revealed that high-strength concrete could mitigate the concrete damage and residual deformation after an earthquake, and that the concrete strength and steel bar strength should be matched when enhancing the seismic resilience of precast columns with high-strength steel bars. It was determined that increasing the prestress mechanism, namely the ratio of the UPTs, could greatly improve the residual deformation, while the ratio of ED bars is the key factor in enhancing the energy dissipation capacity of the precast columns. Suitable ratios of UPTs and ED bars are the keys to ensuring stable energy dissipation and low residual drifts. Moreover, an increased axial load ratio and prestress level are able to restrain the joint opening and improve the bearing capacity of the precast columns; however, an excessive axial load or prestressing force would result in the rapid degeneration of the carrying capacity and larger residual displacements.

Identification of Species-Specific Prey Uptake and Biotransformation of Chiral Polychlorinated Biphenyls (PCBs) in Riparian and Aquatic Food Webs.

The atropisomeric enrichment of chiral polychlorinated biphenyls (PCBs) can trace the movement of PCBs through food webs, but it is a challenge to elucidate the prey uptake and stereoselective biotransformation of PCBs in different species. The present study investigated the concentrations and enantiomer fractions (EFs) of chiral PCBs in invertebrates, fishes, amphibians, and birds. Chiral PCB signature was estimated in total prey for different predators based on quantitative prey sources. The nonracemic PCBs in snakehead (Ophiocephalus argus) were mainly from prey. EFs of PCBs in amphibians and birds were mainly influenced by biotransformation, which showed enrichment of (+)-CBs 132 and 135/144 and different enantiomers of CBs 95 and 139/149. Biomagnification factors (BMFs) of chiral PCBs were higher than 1 for amphibians and passerine birds and lower than 1 for kingfisher (Alcedo atthis) and snakehead. BMFs were significantly correlated with EFs of chiral PCBs in predators and indicative of atropisomeric enrichment of PCBs across different species. Trophic magnification factors (TMFs) were higher in the riparian food web than in the aquatic food web because of the high metabolism capacity of chiral PCBs in aquatic predators. The results highlight the influences of species-specific prey sources and biotransformation on the trophic dynamics of chiral PCBs.

Diatomic iron nanozyme with lipoxidase-like activity for efficient inactivation of enveloped virus.

Enveloped viruses encased within a lipid bilayer membrane are highly contagious and can cause many infectious diseases like influenza and COVID-19, thus calling for effective prevention and inactivation strategies. Here, we develop a diatomic iron nanozyme with lipoxidase-like (LOX-like) activity for the inactivation of enveloped virus. The diatomic iron sites can destruct the viral envelope via lipid peroxidation, thus displaying non-specific virucidal property. In contrast, natural LOX exhibits low antiviral performance, manifesting the advantage of nanozyme over the natural enzyme. Theoretical studies suggest that the Fe-O-Fe motif can match well the energy levels of Fe2 minority ß-spin d orbitals and pentadiene moiety π* orbitals, and thus significantly lower the activation barrier of cis,cis-1,4-pentadiene moiety in the vesicle membrane. We showcase that the diatomic iron nanozyme can be incorporated into air purifier to disinfect airborne flu virus. The present strategy promises a future application in comprehensive biosecurity control.

Use of Nanoindentation in Determination of Regional Biomechanical Properties of Rabbit Cornea After UVA Cross-Linking.

Purpose: To evaluate the regional effects of different corneal cross-linking (CXL) protocols on corneal biomechanical properties. Methods: The study involved both eyes of 50 rabbits, and the left eyes were randomized to the five intervention groups, which included the standard CXL group (SCXL), which was exposed to 3-mW/cm2 irradiation, and three accelerated CXL groups (ACXL1-3), which were exposed to ultraviolet-A at irradiations of 9 mW/cm2, 18 mW/cm2, and 30 mW/cm2, respectively, but with the same total dose (5.4 J/cm2). A control (CO) group was not exposed to ultraviolet-A. No surgery was done on the contralateral eyes. The corneas of each group were evaluated by the effective elastic modulus (Eeff) and the hydraulic conductivity (K) within a 7.5-mm radius using nanoindentation measurements. Results: Compared with the CO group, Eeff (in regions with radii of 0-1.5 mm, 1.5-3.0 mm, and 3.0-4.5 mm) significantly increased by 309%, 276%, and 226%, respectively, with SCXL; by 222%, 209%, and 173%, respectively, with ACXL1; by 111%, 109%, and 94%, respectively, with ACXL2; and by 59%, 41%, and 37%, respectively, with ACXL3 (all P < 0.05). K was also significantly reduced by 84%, 81%, and 78%, respectively, with SCXL; by 75%, 74%, and 70%, respectively, with ACXL1; by 64%, 62%, and 61%, respectively, with ACXL2; and by 33%, 36%, and 32%, respectively, with ACXL3 (all P < 0.05). For the other regions(with radii between 4.5 and 7.5 mm), the SCXL and ACXL1 groups (but not the ACXL2 and ACXL3 groups) still showed significant changes in Eeff and K. Conclusions: CXL had a significant effect on corneal biomechanics in both standard and accelerated procedures that may go beyond the irradiated area. The effect of CXL in stiffening the tissue and reducing permeability consistently decreased with reducing the irradiance duration.

Ir-Sn pair-site triggers key oxygen radical intermediate for efficient acidic water oxidation.

The anode corrosion induced by the harsh acidic and oxidative environment greatly restricts the lifespan of catalysts. Here, we propose an antioxidation strategy to mitigate Ir dissolution by triggering strong electronic interaction via elaborately constructing a heterostructured Ir-Sn pair-site catalyst. The formation of Ir-Sn dual-site at the heterointerface and the resulting strong electronic interactions considerably reduce d-band holes of Ir species during both the synthesis and the oxygen evolution reaction processes and suppress their overoxidation, enabling the catalyst with substantially boosted corrosion resistance. Consequently, the optimized catalyst exhibits a high mass activity of 4.4 A mgIr-1 at an overpotential of 320 mV and outstanding long-term stability. A proton-exchange-membrane water electrolyzer using this catalyst delivers a current density of 2 A cm-2 at 1.711 V and low degradation in an accelerated aging test. Theoretical calculations unravel that the oxygen radicals induced by the π* interaction between Ir 5d-O 2p might be responsible for the boosted activity and durability.

Selective CO2 Reduction to Ethylene Mediated by Adaptive Small-molecule Engineering of Copper-based Electrocatalysts.

Electrochemical CO2 reduction reaction (CO2 RR) over Cu catalysts exhibits enormous potential for efficiently converting CO2 to ethylene (C2 H4 ). However, achieving high C2 H4 selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO2 RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu-based material to a pathway that facilitates CO2 reduction to C2 H4 products. An excellent Faraday efficiency (FE) of 63.6 % on C2 H4 with a current density of 497.2 mA cm-2 in flow cell was achieved, about 6.5 times higher than the pristine Cu catalyst which mainly produce CH4 . The in situ X-ray absorption spectroscopy and Raman studies reveal that the hydroxyl group in TA stabilizes Cuδ+ during the CO2 RR. Furthermore, theoretical calculations demonstrate that the Cuδ+ /Cu0 interfaces lower the activation energy barrier for *CO dimerization, and hydroxyl species stabilize the *COH intermediate via hydrogen bonding, thereby promoting C2 H4 production. Such molecule engineering modulated electronic structure provides a promising strategy to achieve highly selective CO2 reduction to value-added chemicals.

circPSD3 is a promising inhibitor of uPA system to inhibit vascular invasion and metastasis in hepatocellular carcinoma.

BACKGROUND: Vascular invasion is a major route for intrahepatic and distant metastasis in hepatocellular carcinoma (HCC) and is a strong negative prognostic factor. Circular RNAs (circRNAs) play important roles in tumorigenesis and metastasis. However, the regulatory functions and underlying mechanisms of circRNAs in the development of vascular invasion in HCC are largely unknown. METHODS: High throughput sequencing was used to screen dysregulated circRNAs in portal vein tumor thrombosis (PVTT) tissues. The biological functions of candidate circRNAs in the migration, vascular invasion, and metastasis of HCC cells were examined in vitro and in vivo. To explore the underlying mechanisms, RNA sequencing, MS2-tagged RNA affinity purification, mass spectrometry, and RNA immunoprecipitation assays were performed. RESULTS: circRNA sequencing followed by quantitative real-time PCR (qRT-PCR) revealed that circRNA pleckstrin and Sect. 7 domain containing 3 (circPSD3) was significantly downregulated in PVTT tissues. Decreased circPSD3 expression in HCC tissues was associated with unfavourable characteristics and predicted poor prognosis in HCC. TAR DNA-binding protein 43 (TDP43) inhibited the biogenesis of circPSD3 by interacting with the downstream intron of pre-PSD3. circPSD3 inhibited the intrahepatic vascular invasion and metastasis of HCC cells in vitro and in vivo. Serpin family B member 2 (SERPINB2), an endogenous bona fide inhibitor of the urokinase-type plasminogen activator (uPA) system, is the downstream target of circPSD3. Mechanistically, circPSD3 interacts with histone deacetylase 1 (HDAC1) to sequester it in the cytoplasm, attenuating the inhibitory effect of HDAC1 on the transcription of SERPINB2. In vitro and in vivo studies demonstrated that circPSD3 is a promising inhibitor of the uPA system. CONCLUSIONS: circPSD3 is an essential regulator of vascular invasion and metastasis in HCC and may serve as a prognostic biomarker and therapeutic target.