Search

This study investigates the evolution of superconductivity in K2-xFe4+ySe5 using temperature-dependent X-ray absorption and resonant inelastic X-ray scattering techniques. Magnetization measurements show that polycrystalline superconducting (SC) K1.9Fe4.2Se5 has a critical temperature (T c) of ∼31 K with a varying superconducting volume fraction, which strongly depends on its synthesis temperature. An increase in Fe-structural/vacancy disorder in SC samples with more Fe atoms occupying vacant 4d sites is found to be closely related to the decrease in the spin magnetic moment of Fe. Moreover, the nearest-neighbor Fe-Se bond length in SC samples exceeds that in the non-SC (NS) sample, K2Fe4Se5, which indicates a weaker hybridization between the Fe 3d and Se 4p states in SC samples. These results clearly demonstrate the correlations among the local electronic and atomic structures and the magnetic properties of K2-xFe4+ySe5 superconductors, providing deeper insight into the electron pairing mechanisms of superconductivity.

This study investigates the evolution of superconductivity in K2-xFe4+ySe5 using temperature-dependent X-ray absorption and resonant inelastic X-ray scattering techniques. Magnetization measurements show that polycrystalline superconducting (SC) K1.9Fe4.2Se5 has a critical temperature (T c) of ∼31 K with a varying superconducting volume fraction, which strongly depends on its synthesis temperature. An increase in Fe-structural/vacancy disorder in SC samples with more Fe atoms occupying vacant 4d sites is found to be closely related to the decrease in the spin magnetic moment of Fe. Moreover, the nearest-neighbor Fe-Se bond length in SC samples exceeds that in the non-SC (NS) sample, K2Fe4Se5, which indicates a weaker hybridization between the Fe 3d and Se 4p states in SC samples. These results clearly demonstrate the correlations among the local electronic and atomic structures and the magnetic properties of K2-xFe4+ySe5 superconductors, providing deeper insight into the electron pairing mechanisms of superconductivity.

X-ray absorption spectroscopy (XAS) is performed to study changes in the electronic structures of colossal magnetoresistance (CMR) and charged ordered (CO) La1-x Ca x MnO3 manganites with respect to temperature. The pre-edge features in O and Mn K-edge XAS spectra, which are highly sensitive to the local distortion of MnO6 octahedral, exhibit contrasting temperature dependence between CMR and CO samples. The seemingly counter-intuitive XAS temperature dependence can be reconciled in the context of polarons. These results help identify the most relevant orbital states associated with polarons and highlight the crucial role played by polarons in understanding the electronic structures of manganites.

X-ray absorption spectroscopy (XAS) is performed to study changes in the electronic structures of colossal magnetoresistance (CMR) and charged ordered (CO) La1-x Ca x MnO3 manganites with respect to temperature. The pre-edge features in O and Mn K-edge XAS spectra, which are highly sensitive to the local distortion of MnO6 octahedral, exhibit contrasting temperature dependence between CMR and CO samples. The seemingly counter-intuitive XAS temperature dependence can be reconciled in the context of polarons. These results help identify the most relevant orbital states associated with polarons and highlight the crucial role played by polarons in understanding the electronic structures of manganites.

Previous studies on acetaldehyde dehydrogenase 2 (ALDH2) focused on drinking behavior or alcoholism because the ALDH2*2 allele protects against the risk of developing alcoholism. The mechanism provides that the ALDH2 gene's protective effect is also involved in dopamine metabolism. The interaction of the ALDH2 gene with neurotransmitters, such as dopamine, is suggested to be related to alcoholism. Because alcoholism is often co-morbid with antisocial personality disorder (ASPD), previous association studies on antisocial alcoholism cannot differentiate whether those genes relate to ASPD with alcoholism or ASPD only. This study examined the influence of the interaction effect of the ALDH2*1*1, *1*2 or *2*2 polymorphisms with the dopamine 2 receptor (DRD2) Taq I polymorphism on ASPD. Our 541 Han Chinese male participants were classified into three groups: antisocial alcoholism (ASPD co-morbid with alcohol dependence, antisocial ALC; n = 133), ASPD without alcoholism (ASPD not co-morbid with alcohol dependence, antisocial non-ALC; n = 164) and community controls (healthy volunteers from the community; n = 244). Compared with healthy controls, individuals with the DRD2 A1/A1 and the ALDH2*1/*1 genotypes were at a 5.39 times greater risk for antisocial non-ALC than were those with other genotypes. Our results suggest that the DRD2/ANKK1 and ALDH2 genes interacted in the antisocial non-ALC group; a connection neglected in previous studies caused by not separating antisocial ALC from ASPD. Our study made this distinction and showed that these two genes may be associated ASPD without co-morbid alcoholism. [ABSTRACT FROM AUTHOR]

Backgrounds: Imatinib mesylate (STI-571), a tyrosine kinase inhibitor, has previously been demonstrated to attenuate liver fibrogenesis through inhibition of the activation of hepatic stellate cells (HSCs) in CCL(4)-treated rat models.Aims: This study aimed to further evaluate the role of STI-571 in liver regeneration.Materials and Methods: All animals were divided into four groups, and mice were treated with or without CCL(4) and STI-571 (n = 6 for each group).Results: Activated cultured HSCs in vitro with STI-571 administration showed increased apoptosis and reduced proliferation, as determined by flow cytometric analysis, 3-(4, 5-cimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide assay, and confocal microscopy. STI-571 treatment attenuated liver fibrosis in vivo, as was evident in the results of histology, mRNA level, and expression analysis of smooth muscle actin and type I collagen. Mice treated with STI-571 had increased liver weight ratio and the improvement in liver regeneration was compatible with the change of serum interleukin 6 levels (p < 0.05). Further, increased apoptosis and a reduced proliferation were observed in the CCL(4)-treated mice after STI-571 treatment based on the immunohistochemical staining of Annexin V, phosphorylated STAT3, and PCNA.Conclusion: STI-571 treatment effectively attenuated liver fibrogenesis and improved in liver regeneration in vivo and induced apoptosis in HSCs both in vitro and in vivo. [ABSTRACT FROM AUTHOR]

BACKGROUND: suggested that the genetic variation at ADH1B and ALDH2 influences the risk of alcoholism. The ADH1B*2 and ALDH2*2 alleles had been thought to be protective against alcoholism. Recent studies have suggested that either physiological tolerance of blood acetaldehyde, or innate insensitivity to it, or both may play a crucial role in keeping alcoholism from developing by protecting against adverse reactions. ALDH inactive form resulting from ALDH2*2, which slows the elimination of acetaldehyde and the more active isozymes produced by ADH1B*2, could generate higher acetaldehyde levels and thus deter heavy drinking (). The genotype frequency of ADH1B*2/*2 and ALDH2*(1/*2 or 2/*2), which are regarded protective against drinking behavior, is about 70% and 50%, respectively, among the Han Chinese population in Taiwan (Chen et al., 1999a). Most previous studies, however, have failed to separate the effects of antisocial personality disorder from those of alcoholism because of their high comorbidity. To understand the relationship among alcoholism, antisocial personality disorder, and the protective effects of ADH and ALDH, it is necessary to recruit individuals with antisocial personality disorder but without alcoholism. This study was designed to stratify subjects by various ADH1B and ALDH2 genotypes for a more effective association study. The strata were: antisocial alcoholics, antisocial non-alcoholics, community alcoholics, and normal controls. METHODS: We recruited 579 Han Chinese individuals in Taiwan, intending to examine the alcoholism-protection effects of different ADH1B and ALDH2 genotypes with or without antisocial personality disorder. RESULTS: We found no difference of ADH1B*2 allele frequency between the subjects of antisocial alcoholism and subjects of antisocial non-alcoholism, but we found significant difference of ALDH2*2 allele between these two groups. CONCLUSIONS: We concluded that there is no alcoholism-protection effect of ADH1B*2 allele in antisocial alcoholics among Han Chinese in Taiwan. [ABSTRACT FROM AUTHOR]

CD26, a 110 kDa cell surface glycoprotein, exhibits dipeptidyl peptidase IV (DPPIV; EC 2.4.14.5) enzyme activity and plays an important role in T cell co-stimulation. In the present study, the function of CD26/DPPIV in transendothelial migration was examined using β-chemokines as chemoattractants. When soluble recombinant CD26 (sCD26/DPPIV+) was added to the transendothelial chemotaxis system, chemotactic migration of T cells toward RANTES was significantly enhanced. Addition of sCD26 to 50 ng/mol of RANTES enhanced the migratory response by a factor of two compared to RANTES alone, whereas mutant soluble CD26 (mCD26), lacking the DPPIV enzyme activity, had no enhancing effect on RANTES-induced T cell migration. In the process of analyzing the mechanisms of the enhancement of T cell migration by sCD26, we showed that RANTES was cleaved by sCD26 under physiologic conditions at the precise site characteristic of its enzyme specificity. However, synthesized RANTES which lacks two N-terminal amino acids showed a chemotactic activity equivalent to full-length RANTES on T cells. Furthermore, addition of sCD26 showed enhancement of T cell migration induced by both forms of RANTES. In contrast to T cells, the truncated RANTES is inactive in chemotaxis of purified monocytes and supplement of sCD26 but not mCD26 reduced the migratory response of monocytes to RANTES. These results suggest that CD26/DPPIV differentially regulate the chemotactic response of T cells and monocytes to RANTES. [ABSTRACT FROM PUBLISHER]

Rechargeable zinc-air batteries (ZABs) are viewed as a promising solution for electric vehicles due to their potential to provide a clean, cost-effective, and sustainable energy storage system for the next generation. Nevertheless, sluggish kinetics of the oxygen evolution reaction (OER), the oxygen reduction reaction (ORR) at the air electrode, and low power density are significant challenges that hinder the practical application of ZABs. The key to resolving the development of ZABs is developing an affordable, efficient, and stable catalyst with bifunctional catalytic. In this study, we present a series of bifunctional catalysts composed of Co/Zn nanoparticles uniformly embedded in nitrogen-doped carbon (NC) and multi-walled carbon nanotubes (MWCNTs) denoted as Co/Zn@NC@MWCNTs. The incorporation of MWCNTs using a facile and non-toxic method significantly decreased the overpotential of the OER from 570 to 430 mV at 10 mA cm -2 and the peak power density from 226 to 263 mW cm -2 . Besides, the electrochemical surface area measurements and electrochemical impedance spectroscopy indicate that the three-dimensional (3D) network structure of MWCNTs facilitates mass transport for ORR and reduces electron transfer resistance during OER, leading to a small potential gap of 0.86 V between OER and ORR, high electron transfer number (3.92-3.98) of the ORR, and lowest Tafel slope (47.8 mV dec -1 ) of the OER in aqueous ZABs. In addition, in-situ Raman spectroscopy revealed a notable decrease in the I D /I G ratio for the optimally configured Co/Zn@NC@MWCNTs (75:25), indicating a reduction in defect density and improved structural ordering during the electrochemical process, which directly contributes to enhanced ORR activity. Hence, this study provides an excellent strategy for constructing a bifunctional catalyst material with a 3D MWCNTs conductive network for the development of advanced ZAB systems for sustainable energy applications., 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 © 2024 Elsevier Inc. All rights reserved.)

Objective: To characterize patients referred for diabetic retinopathy (DR) screening in a unique multidisciplinary diabetes care clinic at a tertiary care centre., Methods: A retrospective study was conducted involving patients who were referred to the Cardiac and Renal Endocrine Clinic at a tertiary care centre (University Health Network) for DR screening between April 2019-March 2020 and November 2020-August 2021. Patients' demographics; micro- and macrovascular disease measurements; visual acuity, intraocular pressure, fundus imaging, and optical coherence tomography results were collected and analyzed., Results: Of the 64 patients who attended the clinic, 21 patients (33%) with type 2 diabetes had on-site DR screening. The remaining 43 patients had DR screening within 6 months of the appointment or were under ophthalmology care with annual screening visits elsewhere. Of the 21 patients who underwent retinopathy screening, 7 patients (33%) had DR: 4 had mild nonproliferative DR, 2 had moderate nonproliferative DR, 1 had proliferative DR, and 1 had macular edema. Patients with DR had a significantly longer diabetes duration than patients without DR (24.5 ± 10.2 years vs 12.5 ± 5.8 years; p = 0.0247). No significant differences were observed in glycemic control, blood pressure, lipid profiles, kidney function, visual acuity, or intraocular pressure., Conclusions: Our analysis suggests a potential benefit of integrated DR screening in patients with long-standing diabetes as part of a multidisciplinary diabetes care clinic to diagnose and manage DR. Future work is needed to further develop such clinics and investigate their long-term effect on patient outcomes., (Copyright © 2023 Canadian Ophthalmological Society. Published by Elsevier Inc. All rights reserved.)

Despite the unique advantages of single-atom catalysts, molecular dual-active sites facilitate the C-C coupling reaction for C 2 products toward the CO 2 reduction reaction (CO 2 RR). The Ni/Cu proximal dual-active site catalyst (Ni/Cu-PASC) is developed, which is a harmonic catalyst with dual-active sites, by simply mixing commercial Ni-phthalocyanine (Ni-Pc) and Cu-phthalocyanine (Cu-Pc) molecules physically. According to scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) energy dispersive spectroscopy (EDS) data, Ni and Cu atoms are separated, creating dual-active sites for the CO 2 RR. The Ni/Cu-PASC generates ethanol with an FE of 55%. Conversely, Ni-Pc and Cu-Pc have only detected single-carbon products like CO and HCOO - . In situ X-ray absorption spectroscopy (XAS) indicates that CO generation is caused by the stable Ni active site's balanced electronic state. The CO production from Ni-Pc consistently increased the CO concentration over Cu sites attributed to subsequent reduction reaction through a C-C coupling on nearby Cu. The CO bound (HCOO - ) peak, which can be found on Cu-Pc, vanishes on Ni/Cu-PASC, as shown by in situ fourier transformation infrared (FTIR). The characteristic intermediate of *CHO instead of HCOO - proves to be the prerequisite for multi-carbon products by electrochemical CO 2 RR. The work demonstrates that the harmonic dual-active sites in Ni/Cu-PASC can be readily available by the cascading proximal active Ni- and Cu-Pc sites., (© 2023 Wiley‐VCH GmbH.)

A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO 2 cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O 2 synthesis and subsequent atomic layer deposition of a unique ultrathin Li x Al y Zn z O δ protective layer comprising a Li x Al y Zn z O δ surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm -2 ), a high specific cathode capacity (203 mAh g -1 ), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g -1 at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

Realizing viable electrocatalytic processes for energy conversion/storage strongly relies on an atomic-level understanding of dynamic configurations on catalyst-electrolyte interface. X-ray absorption spectroscopy (XAS) has become an indispensable tool to in situ investigate dynamic natures of electrocatalysts but still suffers from limited energy resolution, leading to significant electronic transitions poorly resolved. Herein, we highlight advanced X-ray spectroscopies beyond conventional XAS, with emphasis on their unprecedented capabilities of deciphering key configurations of electrocatalysts. The profound complementarities of X-ray spectroscopies from various aspects are established in a probing energy-dependent "in situ spectroscopy map" for comprehensively understanding the solid-liquid interface. This perspective establishes an indispensable in situ research model for future studies and offers exciting research prospects for scientists and spectroscopists., (© 2023. Springer Nature Limited.)

Oxygen evolution reaction (OER) plays a key role in proton exchange membrane water electrolysis (PEMWE), yet the electrocatalysts still suffer from the disadvantages of low activity and poor stability in acidic conditions. Here, a new class of CdRu 2 IrO x nanoframes with distorted structure for acidic OER is successfully fabricated. Impressively, CdRu 2 IrO x displays an ultralow overpotential of 189 mV and an ultralong stability of 1500 h at 10 mA cm⁻ 2 toward OER in 0.5 M H 2 SO 4 . Moreover, a PEMWE using the distorted CdRu 2 IrO x can be steadily operated at 0.1 A cm⁻ 2 for 90 h. Microstructural analyses and X-ray absorption spectroscopy (XAS) demonstrate that the synergy between Ru and Ir in CdRu 2 IrO x induces the distortion of Ru-O, Ir-O, and Ru-M (M = Ru, Ir) bonds. In situ XAS indicates that the applied potential leads to the deformation octahedral structure of RuO x /IrO x and the formation of stable Ru 5+ species for OER. Theoretical calculations also reveal that the distorted structures can reduce the energy barrier of rate-limiting step during OER. This work provides an efficient strategy for constructing structural distortion to achieve significant enhancement on the activity and stability of OER catalysts., (© 2023 Wiley-VCH GmbH.)

Spin-polarization is known as a promising way to promote the anodic oxygen evolution reaction (OER), since the intermediates and products endow spin-dependent behaviors, yet it is rarely reported for ferromagnetic catalysts toward acidic OER practically used in industry. Herein, the first spin-polarization-mediated strategy is reported to create a net ferromagnetic moment in antiferromagnetic RuO 2 via dilute manganese (Mn 2+ ) (S = 5/2) doping for enhancing OER activity in acidic electrolyte. Element-selective X-ray magnetic circular dichroism reveals the ferromagnetic coupling between Mn and Ru ions, fulfilling the Goodenough-Kanamori rule. The ferromagnetism behavior at room temperature can be well interpreted by first principles calculations as the interaction between the Mn 2+ impurity and Ru ions. Indeed, Mn-RuO 2 nanoflakes exhibit a strongly magnetic field enhanced OER activity, with the lowest overpotential of 143 mV at 10 mA cm geo -2 and negligible activity decay in 480 h stability (vs 200 mV/195 h without magnetic field) as known for magnetic effects in the literature. The intrinsic turnover frequency is also improved to reach 5.5 s -1 at 1.45 V RHE . This work highlights an important avenue of spin-engineering strategy for designing efficient acidic oxygen evolution catalysts., (© 2023 Wiley-VCH GmbH.)

Ligands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoCl 2 bpy 2 catalyzed Negishi-type cross-coupling. A full catalytic cycle of this kind of reaction was elucidated by multiple spectroscopic studies. The solvent and ligand were found to be essential for the generation of catalytic active Co(I) species, among which acetonitrile and bipyridine ligand are resistant to the disproportionation events of Co(I). Investigations, based on Quick-X-Ray Absorption Fine Structure (Q-XAFS) spectroscopy, Electron Paramagnetic Resonance (EPR), IR allied with DFT calculations, allow comprehensive mechanistic insights that establish the structural information of the catalytic active cobalt species along with the whole catalytic Co(I)/Co(III) cycle. Moreover, the acetonitrile and bipyridine system can be further extended to the acylation, allylation, and benzylation of aryl zinc reagents, which present a broad substrate scope with a catalytic amount of Co salt. Overall, this work provides a basic mechanistic perspective for designing cobalt-catalyzed cross-coupling reactions., (© 2023. The Author(s).)

The development of magnetic adsorbents with high capacity to capture heavy metals has been the subject of intense research, but the process usually involves costive synthesis steps. Here, we propose a green approach to obtaining a magnetic biohybrid through in situ grown anaerobic granular sludge (AGS) with the help of magnetite, constituting a promising adsorbent for sequestration and immobilization of Pb in aqueous solutions and soils. The resultant magnetite-embedded AGS (M-AGS) was not only capable of promoting methane production but also conducive to Pb adsorption because of the large surface area and abundant function groups. The uptake of Pb on M-AGS followed the pseudo-second order, having a maximum adsorption capacity of 197.8 mg gDS -1 at pH 5.0, larger than 159.7, 170.3, and 178.1 mg gDS -1 in relation to AGS, F-AGS (ferrihydrite-mediated), and H-AGS (hematite-mediated), respectively. Mechanistic investigations showed that Pb binding to M-AGS proceeds via surface complexation, mineral precipitation, and lattice replacement, which promotes heavy metal capture and stabilization. This was evident from the increased proportion of structural Pb sequestrated from the aqueous solution and the enhanced percentage of the residual fraction of Pb extracted from the contaminated soils., 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 © 2023 Elsevier Ltd. All rights reserved.)

The increasing need for sustainable acid mine drainage (AMD) treatment has spurred much attention to strategic development of resource recovery. Along this line, we envisage that a coupled electrochemical system involving anodic Fe(II) oxidation and cathodic alkaline production will facilitate in situ synthesis of schwertmannite from AMD. Multiple physicochemical studies showed the successful formation of electrochemistry-induced schwertmannite, with its surface structure and chemical composition closely related to the applied current. A low current (e.g., 50 mA) led to the formation of schwertmannite having a small specific surface area (SSA) of 122.8 m 2 g -1 and containing small amounts of -OH groups (formula Fe 8 O 8 (OH) 4.49 (SO 4 ) 1.76 ), whereas a large current (e.g., 200 mA) led to schwertmannite high in SSA (169.5 m 2 g -1 ) and amounts of -OH groups (formula Fe 8 O 8 (OH) 5.16 (SO 4 ) 1.42 ). Mechanistic studies revealed that the reactive oxygen species (ROS)-mediated pathway, rather than the direct oxidation pathway, plays a dominant role in accelerating Fe(II) oxidation, especially at high currents. The abundance of •OH in the bulk solution, along with the cathodic production of OH - , were the key to obtaining schwertmannite with desirable properties. It was also found to function as a powerful sorbent in removal of arsenic species from the aqueous phase., 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 © 2023 Elsevier B.V. All rights reserved.)

Catalytic reactions are surface-sensitive processes. Fabrication of homogeneous metastable metals can be used to promote phase-dependent catalytic performance; however, this has been a challenging task. Herein, homogeneous metastable hexagonal close-packed (hcp) Ir is epitaxially grown onto metastable phase hcp Ni, as demonstrated using spherical aberration electron microscopy. The as-fabricated metastable hcp Ir exhibits high intrinsic activity for the alkaline hydrogen evolution reaction (HER). In particular, metastable hcp Ir delivers a low overpotential of 17 mV at 10 mA cm -2 and presents a high specific activity of 8.55 mA cm -2 and a high turnover frequency of 38.26 s -1 at -0.07 V versus the reversible hydrogen electrode. Owing to its epitaxially grown structure, metastable hcp Ir is highly stable. Theoretical calculations reveal that metastable hcp Ir promotes H 2 O adsorption and fast H 2 O dissociation, which contributes to its remarkable HER activity. Findings can elucidate the crystal phase-controlled synthesis of advanced noble metal nanomaterials for the fundamental catalytic applications., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

In situ electrochemical reconstruction is important for transition metal oxides explored as electrocatalysts for electrochemical nitrate reduction reactions (ENRRs). Herein, we report substantial performance enhancement of ammonium generation on Co, Fe, Ni, Cu, Ti, and W oxide-based cathodes upon reconstruction. Among them, the performance of a freestanding ER-Co 3 O 4- x /CF (Co 3 O 4 grown on Co foil subjected to electrochemical reduction) cathode was superior to its unreconstructed counterpart and other cathodes; e.g., an ammonium yield of 0.46 mmol h -1 cm -2 , an ammonium selectivity of 100%, and a Faradaic efficiency of 99.9% were attained at -1.3 V in a 1400 mg L -1 NO 3 - -N solution. The reconstruction behaviors were found to vary with the underlying substrate. The inert carbon cloth only acted as a supporting matrix for immobilizing Co 3 O 4 , without appreciable electronic interactions between them. A combination of physicochemical characterizations and theoretical modeling provided compelling evidence that the CF-promoted self-reconstruction of Co 3 O 4 induced the evolution of metallic Co and the creation of oxygen vacancies, which promoted and optimized interfacial nitrate adsorption and water dissociation, thus boosting the ENRR performance. The ER-Co 3 O 4- x /CF cathode performed well over wide ranges of pH and applied current and at high nitrate loadings, ensuring its high efficacy in treating high-strength real wastewater.

The photoinduced transformation of ferrihydrite is an important process that can predict the geochemical cycle of Fe in anoxic environments as well as the fate of trace elements bonded to Fe minerals. We report that the photooxidation of sulfite by UV irradiation produces hydrated electrons (super-reductants), which significantly promote ferrihydrite reduction to Fe(II), and SO 3 •- (a moderate oxidant), enabling its further oxidation to more crystalline Fe(III) products. The experimental results show that the concentration of sulfite was key in influencing the rate and extent of surface-bound Fe(II) formation, which ultimately determined the distribution of individual products. For example, fitting of the Mössbauer spectroscopy data revealed that the relative abundances of mineral species after 8 h of treatment in the UV/sulfite systems were 41.9% lepidocrocite and 58.1% ferrihydrite at 2 mM SO 3 2- ; 41.8% goethite, 28.2% lepidocrocite, and 29.1% ferrihydrite at 5 mM SO 3 2- ; and 100% goethite at 10 mM SO 3 2- . The combined results of the chemical speciation analysis and the Cd K-edge EXAFS characterization provided compelling evidence that Cd was firmly incorporated into the structure of newly formed minerals, particularly at high sulfite concentrations. These findings provide an understanding of the role of UV/sulfite in facilitating ferrihydrite transformation and promoting Cd stabilization in oxygen-deficit soils and aquatic environments., 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 © 2023 Elsevier Ltd. All rights reserved.)

The development of high-performance catalysts with high activity, selectivity, and stability are essential for the practical applications of H 2 O 2 electrosynthesis technology, but it is still formidably challenging. It is reported that the low-coordinated structure of Pd sites in amorphous PdSe 2 nanoparticles (a-PdSe 2 NPs) can significantly boost the electrocatalytic synthesis of H 2 O 2 . Detailed investigations and theoretical calculations reveal that the disordered arrangement of Pd atoms in a-PdSe 2 NPs can promote the activity, while the Pd sites with low-coordinated environment can optimize the adsorption toward oxygenated intermediate and suppress the cleavage of O-O bond, leading to a significant enhancement in both the H 2 O 2 selectivity and productivity. Impressively, a-PdSe 2 NPs/C exhibits high H 2 O 2 selectivity over 90% in different pH electrolytes. H 2 O 2 productivities with ≈3245.7, 1725.5, and 2242.1 mmol g Pd -1  h -1 in 0.1 m KOH, 0.1 m HClO 4 , and 0.1 m Na 2 SO 4 can be achieved, respectively, in an H-cell electrolyzer, being a pH-universal catalyst for H 2 O 2 electrochemical synthesis. Furthermore, the produced H 2 O 2 can reach 1081.8 ppm in a three-phase flow cell reactor after 2 h enrichment in 0.1 m Na 2 SO 4 , showing the great potential of a-PdSe 2 NPs/C for practical H 2 O 2 electrosynthesis., (© 2022 Wiley-VCH GmbH.)

Ni-containing heteropolyvanadate, Na 6 [NiV 14 O 40 ], was synthesized for the first time to be applied in high-energy lithium storage applications as a negative electrode material. Na 6 [NiV 14 O 40 ] can be prepared via a facile solution process that is suitable for low-cost mass production. The as-prepared electrode provided a high capacity of approximately 700 mAh g -1 without degradation for 400 cycles, indicating excellent cycling stability. The mechanism of charge storage was investigated using operando X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), transition X-ray microscopy (TXM), and density functional theory (DFT) calculations. The results showed that V 5+ was reduced to V 2+ during lithiation, indicating that Na 6 [NiV 14 O 40 ] is an insertion-type material. In addition, Na 6 [NiV 14 O 40 ] maintained its amorphous structure with negligible volume expansion/contraction during cycling. Employed as the negative electrode in a lithium-ion battery (LIB), the Na 6 [NiV 14 O 40 ]//LiFePO 4 full cell had a high energy density of 300 W h kg -1 . When applied in a lithium-ion capacitor, the Na 6 [NiV 14 O 40 ]//expanded mesocarbon microbead full cell displayed energy densities of 218.5 and 47.9 W h kg -1 at power densities of 175.7 and 7774.2 W kg -1 , respectively. These findings reveal that the negative electrode material Na 6 [NiV 14 O 40 ] is a promising candidate for Li-ion storage applications.

As the most promising alternative to platinum-based catalysts for cathodic oxygen reduction reaction (ORR) in proton exchange membrane fuel cells, further performance enhancement of Fe-N-C catalysts is highly expected to promote their wide application. In Fe-N-C catalysts, the single Fe atom forms a square-planar configuration with four adjacent N atoms (D 4h symmetry). Breaking the D 4h symmetry of the FeN 4 active center provides a new route to boost the activity of Fe-N-C catalysts. Herein, for the first time, the deformation of the square-planar coordination of FeN 4 moiety achieved by introducing chalcogen oxygen groups (XO 2 , X = S, Se, Te) as polar functional groups in the Fe-N-C catalyst is reported. The theoretical and experimental results demonstrate that breaking the D 4h symmetry of FeN 4 results in the rearrangement of Fe 3d electrons and increases spin moment of Fe centers. The efficient spin state manipulation optimizes the adsorption energetics of ORR intermediates, thereby significantly promoting the intrinsic ORR activity of Fe-N-C catalysts, among which the SeO 2 modified catalyst lies around the peak of the ORR volcano plot. This work provides a new strategy to tune the local coordination and thus the electronic structure of single-atom catalysts., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The B-site Fe/Os ordered and disordered quadruple perovskite oxides CaCu 3 Fe 2 Os 2 O 12 were synthesized under different high-pressure and high-temperature conditions. The B-site ordered CaCu 3 Fe 2 Os 2 O 12 is a system with a very high ferrimagnetic ordering temperature of 580 K having the Cu 2+ (↑)Fe 3+ (↑)Os 5+ (↓) charge and spin arrangement. In comparison, the highly disordered CaCu 3 Fe 2 Os 2 O 12 has a reduced magnetic transition temperature of about 350 K. The Cu 2+ Fe 3+ Os 5+ charge combination remains the same without any sign of changes in the valence state of the constituent ions. Although the average net moments of each sublattice are reduced, the average ferrimagnetic spin arrangement is unaltered. The robustness of the basic magnetic properties of CaCu 3 Fe 2 Os 2 O 12 against site disorder may be taken as an indication of the tendency to maintain the short-range order of the atomic constituents.

Clinical prediction models typically make point estimates of risk. However, values of key variables are often missing during model development or at prediction time, meaning that the point estimates mask significant uncertainty and can lead to over-confident decision making. We present a model of mortality risk in emergency laparotomy which instead presents a distribution of predicted risks, highlighting the uncertainty over the risk of death with an intuitive visualisation. We developed and validated our model using data from 127134 emergency laparotomies from patients in England and Wales during 2013-2019. We captured the uncertainty arising from missing data using multiple imputation, allowing prospective, patient-specific imputation for variables that were frequently missing. Prospective imputation allows early prognostication in patients where these variables are not yet measured, accounting for the additional uncertainty this induces. Our model showed good discrimination and calibration (95% confidence intervals: Brier score 0.071-0.078, C statistic 0.859-0.873, calibration error 0.031-0.059) on unseen data from 37 hospitals, consistently improving upon the current gold-standard model. The dispersion of the predicted risks varied significantly between patients and increased where prospective imputation occurred. We present a case study that illustrates the potential impact of uncertainty quantification on clinical decision making. Our model improves mortality risk prediction in emergency laparotomy and has the potential to inform decision-makers and assist discussions with patients and their families. Our analysis code was robustly developed and is publicly available for easy replication of our study and adaptation to predicting other outcomes., (© 2022. The Author(s).)

Purpose: This study was performed to evaluate the outcome of implementation of transanal total mesorectal excision (TaTME) for low rectal cancer in a regional hospital and in comparison to laparoscopic (Lap) TME., Methods: Consecutive patients with low rectal cancer of which the lowest border of the tumour was located beween 1 and 5 cm from the puborectalis who underwent TME at North District Hospital between January 2013 and December 2019 were included. Clinical, operative, and pathologic outcomes were compared between Lap TME and TaTME. The primary end point was complication profile., Results: Thirty-five patients underwent Lap TME and 45 patients underwent TaTME for low rectal cancer. The conversion rate of the TaTME group was significantly lower than that of the Lap TME group (4.4% vs. 20%, P=0.029), but the operating time was longer (259 minutes vs. 219 minutes, P=0.009). The tumour location was significantly lower in the TaTME group, but the distal resection margins were adequate and not different between both groups. The TaTME group had higher incidence rates of prolonged ileus and urinary tract infection, but the other complications were similar between the two groups. The resection margin positivity rates of the TaTME and Lap TME groups were 2.2% and 5.7%, respectively (P=0.670). At a median follow up of 39 months, no abnormal early recurrence was detected., Conclusion: It is technically feasible and oncologically safe to perform TaTME in a medium-volume colorectal unit. Patients with difficult pelvic anatomy can benefit by reducing the risk of conversion and margin positivity rate.

Obesity is now considered a primary comorbidity in heart failure with preserved ejection fraction (HFpEF) pathophysiology, mediated largely by systemic inflammation. Although there is accumulating evidence for a disease-related dysregulation of blood flow during exercise in this patient group, the role of obesity in the hemodynamic response to exercise remains largely unknown. Small muscle mass handgrip (HG) exercise was used to evaluate exercising muscle blood flow in nonobese (BMI < 30 kg/m 2 , n = 14) and obese (BMI > 30 kg/m 2 , n = 40) patients with HFpEF. Heart rate (HR), stroke index (SI), cardiac index (CI), mean arterial pressure (MAP), forearm blood flow (FBF), and vascular conductance (FVC) were assessed during progressive intermittent HG exercise [15%-30%-45% maximal voluntary contraction (MVC)]. Blood biomarkers of inflammation [C-reactive protein (CRP) and interleukin-6 (IL-6)] were also determined. Exercising FBF was reduced in obese patients with HFpEF at all work rates (15%: 304 ± 42 vs. 229 ± 15 mL/min; 30%: 402 ± 46 vs. 300 ± 18 mL/min; 45%: 484 ± 55 vs. 380 ± 23 mL/min, nonobese vs. obese, P = 0.025), and was negatively correlated with BMI ( R = -0.47, P < 0.01). In contrast, no differences in central hemodynamics (HR, SI, CI, and MAP) were found between groups. Proinflammatory biomarkers were markedly elevated in patients with obesity (CRP: 2,133 ± 418 vs. 4,630 ± 590 ng/mL, P = 0.02; IL-6: 2.9 ± 0.3 vs. 5.2 ± 0.7 pg/mL, nonobese vs. obese, P = 0.04), and both biomarkers were positively correlated with BMI (CRP: R = 0.40, P = 0.03; IL-6: R = 0.57, P < 0.01). Together, these findings demonstrate the presence of obesity and an accompanying milieu of systemic inflammation as important factors in the dysregulation of exercising muscle blood flow in patients with HFpEF. NEW & NOTEWORTHY Obesity is the primary comorbid condition in HFpEF pathophysiology, but the role of adiposity on the peripheral circulation is not well understood. The present study identified a 30%-40% reduction in forearm blood flow during handgrip exercise, accompanied by a marked elevation in proinflammatory plasma biomarkers, in obese patients with HFpEF compared with their nonobese counterparts. These findings suggest an exaggerated dysregulation in exercising muscle blood flow associated with the obese HFpEF phenotype.

Amorphous materials have attracted increasing attention in diverse fields due to their unique properties, yet their controllable fabrications still remain great challenges. Here, we demonstrate a top-down strategy for the fabrications of amorphous oxides through the amorphization of hydroxides. The versatility of this strategy has been validated by the amorphizations of unitary, binary and ternary hydroxides. Detailed characterizations indicate that the amorphization process is realized by the variation of coordination environment during thermal treatment, where the M-OH octahedral structure in hydroxides evolves to M-O tetrahedral structure in amorphous oxides with the disappearance of the M-M coordination. The optimal amorphous oxide (FeCoSn(OH) 6 -300) exhibits superior oxygen evolution reaction (OER) activity in alkaline media, where the turnover frequency (TOF) value is 39.4 times higher than that of FeCoSn(OH) 6 . Moreover, the enhanced OER performance and the amorphization process are investigated with density functional theory (DFT) and molecule dynamics (MD) simulations. The reported top-down fabrication strategy for fabricating amorphous oxides, may further promote fundamental research into and practical applications of amorphous materials for catalysis., (© 2022. The Author(s).)

Background: Patients with diabetes and co-existing chronic kidney disease and/or cardiovascular disease have complex medical needs with multiple indications for different guideline-directed medical therapies and require high health care resource utilization. The Cardiac and Renal Endocrine Clinic (C.a.R.E. Clinic) is a multi- and interdisciplinary clinic offering a unique care model to this population to overcome barriers to optimal care., Objective: To describe the patient characteristics and clinical data of consecutive patients seen in the C.a.R.E. Clinic between 2014 and 2020, with a focus on the feasibility, strengths, and challenges of this outpatient care model., Design: Single-center retrospective cohort study., Setting: The C.a.R.E. Clinic is a multi- and interdisciplinary clinic at Toronto General Hospital in Toronto, Canada., Patients: We reviewed the charts of all 118 patients who had been referred to the C.a.R.E. Clinic with type 2 diabetes mellitus, co-existing renal disease, and/or cardiovascular disease., Measurements: Demographic data, medication data, clinic blood pressure measurements, and laboratory data were assessed at the first and last available clinic visit., Methods: Data were extracted via manual chart review of paper and electronic medical records., Results: First and last attended clinic visit data were available for descriptive analysis in 74 patients. There was a significant improvement in low-density lipoprotein (LDL) cholesterol (1.9 mmol/L vs 1.5 mmol/L, P < .01), hemoglobin A1C (7.5% vs 7.1%, P = .02), and the proportion of patients with blood pressure at target (52.7% vs 36.5%, P = .04), but not body mass index (29.7 kg/m² vs 29.6 kg/m², P = .15) between the last and first available clinic visits. There was higher uptake in evidence-based medication use including statins (93.2% vs 81.1%, P = .01), SGLT-2i (35.1% vs 4.1%, P < .01), and GLP-1 receptor agonists (13.5% vs 4.1%, P = .02), while RAAS inhibitor use was already high at baseline (81.8% vs 78.4%, P = .56). There remains a significant opportunity for therapy with sodium-glucose cotransporter-2 inhibitors and glucagon-like peptide-1 receptor agonists., Limitations: This is a retrospective chart review lacking a control group, therefore clinical improvements cannot be causally attributed to the clinic alone. New evidence and changes to guideline-recommended therapies also contributed to practice changes during this time period., Conclusions: A multi- and interdisciplinary clinic is a feasible and potentially effective way to improve evidence-based and patient-centered care for patients with diabetes, kidney, and cardiovascular disease., Competing Interests: Declaration of Conflicting Interests: The author(s) declared the following potential conflicts of interest with respect to the research, authorship, and/or publication of this article: D.Z.C. has received honoraria from Boehringer Ingelheim-Lilly, Merck, AstraZeneca, Sanofi, Mitsubishi-Tanabe, Abbvie, Janssen, Bayer, Prometic, BMS, Maze, CSL-Behring, and Novo-Nordisk and has received operational funding for clinical trials from Boehringer Ingelheim-Lilly, Merck, Janssen, Sanofi, AstraZeneca, and Novo-Nordisk. J.A.U. has received speaker/consulting honoraria from Amgen, Boehringer Ingelheim, Janssen, Merck, Novartis, and Sanofi and has received grant support to his institutions from AstraZeneca, Bayer, Boehringer Ingelheim, Janssen, Novartis, and Sanofi. M.F. has received research grant support from Amgen, Novartis, and Novo-Nordisk. The other authors report no disclosures., (© The Author(s) 2022.)

We report an electrocatalyst, Co bases (metallic Co and Co(OH) 2 ) with fluoride-incorporated CoO coating on the surface of (CoO-F/Co), was synthesized by the electro-deposition method. The porous network architecture of CoO-F/Co on the glassy carbon electrode exhibited an ultra-low overpotential of 15 mV, achieving the geometric current density of 10 mA cm -2 in 1.0 M KOH, which were comparable with the HER performance of numerous reported noble metal electrocatalysts. It is demonstrated that fluoride incorporation improved the electrodeposition particle size, electronic density, conductivity and hydrophilicity of CoO-F/Co the HER performance.

Zinc ion batteries have been extensively studied with an aqueous electrolyte system. However, the batteries suffer from a limited potential window, gas evolution, cathode dissolution, and dendrite formation on the anode. Considering these limitations, we developed an alternative electrolyte system based on deep eutectic solvents (DESs) because of their low cost, high stability, biodegradability, and non-flammability, making them optimal candidates for sustainable batteries. The DES electrolyte enables reversible Zn plating/stripping and effectively suppresses zinc dendrite formation. Furthermore, in-depth characterizations reveal that the energy storage mechanism can be attributed to [ZnCl] + ion intercalation and the intermediate complex ion plays a pivotal role in electrochemical reactions, which deliver a high reversible capacity of 310 mAh g -1 at 0.1 A g -1 and long-term stability (167 mAh g -1 at a current density of 0.3 A g -1 after 300 cycles, Coulombic efficiency: ∼98%). Overall, this work represents our new finding in rechargeable batteries with the DES electrolyte.