Electrocatalytic water-to-oxygenates conversion: redox-mediated versus direct oxygen transfer.

Electrocatalytic oxygenation of hydrocarbons with high selectivity has attracted much attention for its advantages in the sustainable and controllable production of oxygenated compounds with reduced greenhouse gas emissions. Especially when utilizing water as an oxygen source, by constructing a water-to-oxygenates conversion system at the anode, the environment and/or energy costs of producing oxygenated compounds and hydrogen energy can be significantly reduced. There is a broad consensus that the generation and transformation of oxygen species are among the decisive factors determining the overall efficiency of oxygenation reactions. Thus, it is necessary to elucidate the oxygen transfer process to suggest more efficient strategies for electrocatalytic oxygenation. Herein, we introduce oxygen transfer routes through redox-mediated pathways or direct oxygen transfer methods. Especially for the scarcely investigated direct oxygen transfer at the anode, we aim to detail the strategies of catalyst design targeting the efficient oxygen transfer process including activation of organic substrate, generation/adsorption of oxygen species, and transformation of oxygen species for oxygenated compounds. Based on these examples, the significance of balancing the generation and transformation of oxygen species, tuning the states of organic substrates and intermediates, and accelerating electron transfer for organic activation for direct oxygen transfer has been elucidated. Moreover, greener organic synthesis routes through heteroatom transfer and molecular fragment transfer are anticipated beyond oxygen transfer.

Altered functional connectivity subserving expressed emotion environments in schizophrenia: An fNIRS study.

Living in high-expressed emotion (EE) environments, characterized by critical, hostile, or over-involved family attitudes, has been linked to increased relapse rates among individuals with schizophrenia (SZ). In our previous work (Wang et al., 2023), we conducted the first feasibility study of using functional near-infrared spectroscopy (fNIRS) with our developed EE stimuli to examine cortical hemodynamics in SZ. To better understand the neural mechanisms underlying EE environmental factors in SZ, we extended our investigation by employing functional connectivity (FC) analysis with a graph theory approach to fNIRS signals. Relative to healthy controls (N=40), individuals with SZ (N=37) exhibited altered connectivity across the medial prefrontal cortex (mPFC), left ventrolateral prefrontal cortex (vlPFC), and left superior temporal gyrus (STG) while exposed to EE environments. Notably, while individuals with SZ were exposed to high-EE environments, (i) reduced connectivity was observed in these brain regions and (ii) the left vlPFC-STG coupling was found to be associated with the negative symptom severity. Taken together, our FC findings suggest individuals with SZ experience a more extensive disruption in neural functioning and coordination, particularly indicating an increased susceptibility to high-EE environments. This further supports the potential utility of integrating fNIRS with the created EE stimuli for assessing EE environmental influences, paving the way for more targeted therapeutic interventions.

Electron Divergence of Cuδ- and Pdδ+ in Cu3Pd Alloy-Based Heterojunctions Boosts Concerted C≡C Bond Binding and the Volmer Step for Alkynol Semihydrogenation.

Electrocatalytic semihydrogenation of alkynols presents a sustainable alternative to conventional thermal methodologies for the high-value production of alkenols. The design of efficient catalysts with superior catalytic and energy efficiency for semihydrogenation poses a significant challenge. Here, we present the application of an electron-divergent Cu3Pd alloy-based heterojunction in promoting the electrocatalytic semihydrogenation of alkynols to alkenols using water as the proton source. The tunable electron divergence of Cuδ- and Pdδ+, modulated by rectifying contact with nitrogen-rich carbons, enables the concerted binding of active H species from the Volmer step of water dissociation and the C≡C bond of alkynols on Pdδ+ sites. Simultaneously, the pronounced electron divergence of Cu3Pd facilitates the universal adsorption of OH species from the Volmer step and alkynols on the Cuδ- sites. The electron-divergent dual-center substantially boosts water dissociation and inhibition of completing hydrogen evolution to give a turnover frequency of 2412 h-1, outperforming the reported electrocatalysts' value of 7.3. Moreover, the continuous production of alkenols at industrial-related current density (-200 mA cm-2) over the efficient and durable Cu3Pd-based electrolyzer could achieve a cathodic energy efficiency of 45 mol kW·h-1, 1.7 times the bench-marked reactors, promising great potential for sustainable industrial synthesis.

An elastic single crystal composed of one-dimensional chiral coordination polymers.

A single crystal composed of one-dimensional coordinated polymers, [CdCl2(1-methyl-2-pyridone)]n, has been synthesized and characterized. This compound exhibits outstanding elastic bending due to the molecular spring nature of the CdCl2 coordination framework and weak intermolecular interactions between the coordination chains. Owing to the helical arrangement of organic ligands surrounding the coordination structure, the compound crystallizes in a chiral space group. As a result, it displays compelling circular dichroism spectra and second harmonic generation properties.

DDX3 regulates cancer immune surveillance via 3' UTR-mediated cell-surface expression of PD-L1.

Programmed death-1 (PD-1)/PD ligand-1 (PD-L1)-mediated immune escape contributes to cancer development and has been targeted as an anti-cancer strategy. Here, we show that inhibition of the RNA helicase DDX3 increased CD8+ T cell infiltration in syngeneic oral squamous cell carcinoma tumors. DDX3 knockdown compromised interferon-γ-induced PD-L1 expression and, in particular, reduced the level of cell-surface PD-L1. DDX3 promoted surface PD-L1 expression by recruiting the adaptor protein 2 (AP2) complex to the 3' UTR of PD-L1 mRNA. DDX3 depletion or 3' UTR truncation increased the binding of the coatomer protein complexes to PD-L1, leading to its intracellular accumulation. Therefore, this 3' UTR-dependent mechanism may counteract cellular negative effects on surface trafficking of PD-L1. Finally, pharmaceutic disruption of DDX3's interaction with AP2 reduced surface PD-L1 expression, supporting that the DDX3-AP2 pathway routes PD-L1 to the cell surface. Targeting DDX3 to modulate surface trafficking of immune checkpoint proteins may provide a potential strategy for cancer immunotherapy.

Associations of Proteomics With Hypertension and Systolic Blood Pressure: KORA S4/F4/FF4 and KORA Age1/Age2 Cohort Studies.

BACKGROUND: Hypertension, a complex condition, is primarily defined based on blood pressure readings without involving its pathophysiological mechanisms. We aimed to identify biomarkers through a proteomic approach, thereby enhancing the future definition of hypertension with insights into its molecular mechanisms. METHODS: The discovery analysis included 1560 participants, aged 55 to 74 years at baseline, from the KORA (Cooperative Health Research in the Region of Augsburg) S4/F4/FF4 cohort study, with 3332 observations over a median of 13.4 years of follow-up. Generalized estimating equations were used to estimate the associations of 233 plasma proteins with hypertension and systolic blood pressure (SBP). For validation, proteins significantly associated with hypertension or SBP in the discovery analysis were validated in the KORA Age1/Age2 cohort study (1024 participants, 1810 observations). A 2-sample Mendelian randomization analysis was conducted to infer causalities of validated proteins with SBP. RESULTS: Discovery analysis identified 49 proteins associated with hypertension and 99 associated with SBP. Validation in the KORA Age1/Age2 study replicated 7 proteins associated with hypertension and 23 associated with SBP. Three proteins, NT-proBNP (N-terminal pro-B-type natriuretic peptide), KIM1 (kidney injury molecule 1), and OPG (osteoprotegerin), consistently showed positive associations with both outcomes. Five proteins demonstrated potential causal associations with SBP in Mendelian randomization analysis, including NT-proBNP and OPG. CONCLUSIONS: We identified and validated 7 hypertension-associated and 23 SBP-associated proteins across 2 cohort studies. KIM1, NT-proBNP, and OPG demonstrated robust associations, and OPG was identified for the first time as associated with blood pressure. For NT-proBNP (protective) and OPG, causal associations with SBP were suggested.

Molecular Twist-Induced Single-Crystal Isomerization and Valence Tautomeric Transitions in a Cobalt-Dioxolene Complex.

A mononuclear valence tautomeric (VT) complex, [Co(pycz)2(Sq)(Cat)] (1-trans), where pycz = 9-(pyridin-4-yl)-9H-carbazole, Sq⋅- = 3,5-di-tert-butyl-semiquinonato, and Cat2- = 3,5-di-tert-butyl-catecholato, is synthesized in the trans configuration, which undergoes one-step valence tautomeric transition above room temperature. Remarkably, 1-trans can transform into its isomeric structure, [Co(pycz)2(Sq)(Sq)] (1-cis), at temperature above 350 K in a single-crystal-to-single-crystal way by in situ molecular twist, and the resulting 1-cis exhibits a pronounced two-step VT transition during magnetic measurements that is rare for mononuclear VT complexes. Such drastic solid-state structural transformation is reported in VT compounds for the first time, which is actuated by a crystal surface's melting-recrystallization induced phase transition process. DFT calculations offer an underlying mechanism suggesting a concerted bond rotation during the structural transformation. The results demonstrate an unconventional approach that realizes structural transformation of VT complexes and the control of VT performance.

Interfering TRIB3 protects the blood brain barrier through PI3K/Akt pathway to alleviate cerebral ischemia-reperfusion injury in diabetes mellitus mice.

This study aimed to treat diabetic cerebral ischemia-reperfusion injury (CI/RI) by affecting blood brain barrier (BBB) permeability and integrity. The CI/RI model in DM mice and a high glucose (HG) treated oxygen and glucose deprivation/reoxygenation (OGD/R) brain endothelial cell model were established for the study. Evans blue (EB) staining was used to evaluate the permeability of BBB in vivo. TTC staining was used to analyze cerebral infarction. The location and expression of tribbles homolog 3 (TRIB3) in endothelial cells were detected by immunofluorescence. Western blotting was used to detect the protein expressions of TRIB3, tight junction molecules, adhesion molecules, phosphorylated protein kinase B (p-AKT) and AKT. The levels of pro-inflammatory cytokines were detected by qRT-PCR. Trans-epithelial electrical resistance (TEER) and fluorescein isothiocyanate (FITC)-dextran were used to measure vascular permeability in vitro. TRIB3 ubiquitination and acetylation levels were detected. Acetyltransferase bound to TRIB3 were identified by immunoprecipitation. TRIB3 was localized in cerebral endothelial cells and was highly expressed in diabetic CI/R mice. The BBB permeability in diabetic CI/R mice and HG-treated OGD/R cells was increased, while the junction integrity was decreased. Interference with TRIB3 in vitro reduces BBB permeability and increases junction integrity. In vivo interfering with TRIB3 reduced cerebral infarction volume, BBB permeability and inflammation levels, and upregulated p-AKT levels. The phosphatidylinositol 3-kinase (PI3K) inhibitor wortmannin reversed the effects of TRIB3-interfering plasmid. In vitro HG treatment induced TRIB3 acetylation through acetyltransferase p300, which in turn reduced ubiquitination and stabilized TRIB3. Interfering TRIB3 protects BBB by activating PI3K/AKT pathway and alleviates brain injury, which provides a new target for diabetic CI/RI.

Adaptation cannot keep pace with projected temperature increase.

An emerging argument is that since humans can readily adapt to changing climatic conditions, there is less need to pursue aggressive emissions mitigation strategies. As temperature adaptation is a function of repeated exposure over time, we need empirical approaches that can depict individuals' temperature history to rigorously examine this claim. Using a longitudinal dataset representative of China, we construct lifetime temperature exposure unique to each individual based on their birth-dates, birth-locations, and movement history. We show that a 1°C increase in individualized temperature anomalies cause a 2% decrease in 1 standard deviation (S.D.) of well-being, where most of the impacts are driven by "hotter-than-expected" weather. In turn, while the adverse impacts of future temperature changes wane after accommodating for adaptation, acclimatization is unlikely to keep pace with future temperature increases except in the net-zero emissions scenario, indicating that stringent greenhouse gas (GHG) emissions cuts are still needed even in this less-pessimistic scenario.

Oxidative Amination of Aldehydes with Amines into α-Amino Ketones.

Oxidative amination for the installation of nitrogen functional molecules from nitrogen nucleophiles has always been a very challenging topic in organic synthesis. Here we report a novel conversion of different aldehydes with secondary amines for the synthesis of diversified α-amino ketones. This method can be achieved through oxidative rearrangement of an in situ-generated enamine intermediate promoted by commercially available sodium percarbonate. Furthermore, this one-pot process is also suitable for the functional modification of complex molecules.

Perceptions of the seriousness of major public health problems during the COVID-19 pandemic in seven middle-income countries.

INTRODUCTION: Public perception of the seriousness of the COVID-19 pandemic compared to six other major public health problems (alcoholism and drug use, HIV/AIDS, malaria, tuberculosis, lung cancer and respiratory diseases caused by air pollution and smoking, and water-borne diseases like diarrhea) is unclear. We designed a survey to examine this issue using YouGov's internet panels in seven middle-income countries in Africa, Asia, and Latin America in early 2022. METHODS: Respondents rank ordered the seriousness of the seven health problems using a repeated best-worst question format. Rank-ordered logit models allow comparisons within and across countries and assessment of covariates. RESULTS: In six of the seven countries, respondents perceived other respiratory illnesses to be a more serious problem than COVID-19. Only in Vietnam was COVID-19 ranked above other respiratory illnesses. Alcoholism and drug use was ranked the second most serious problem in the African countries. HIV/AIDS ranked relatively high in all countries. Covariates, particularly a COVID-19 knowledge scale, explained differences within countries; statistics about the pandemic were highly correlated with differences in COVID-19's perceived seriousness. CONCLUSIONS: People in the seven middle-income countries perceived COVID-19 to be serious (on par with HIV/AIDS) but not as serious as other respiratory illnesses. In the African countries, respondents perceived alcoholism and drug use as more serious than COVID-19. Our survey-based approach can be used to quickly understand how the threat of a newly emergent disease, like COVID-19, fits into the larger context of public perceptions of the seriousness of health problems.

We were curious what people in different countries thought about the seriousness of COVID-19 compared to other health problems. We designed a survey, and hired YouGov, a survey research firm, to administer it in seven countries in Africa, Asia, and Latin America in early 2022. Respondents answered the questions on their computer, tablets, or smart phones. Their answers revealed that in most countries respiratory illnesses were perceived to be a more serious problem than COVID-19. In Africa people felt that alcoholism and drug use were also more serious than COVID-19. These findings are important because they show that people still care about the health problems they were facing before the pandemic, which is useful information for healthcare providers.

Ruthenium(v) terminal arylimido corroles: isolation, spectroscopic characterization and reactivity.

Terminal Ru(v)-imido species are thought to be as reactive to group transfer reactions as their Ru(v)-oxo homologues, but are less studied. With the electron-rich corrole ligand, relatively stable and isolable Ru(v)-arylimido complexes [Ru(tBu-Cor)(NAr)] (H3(tBu-Cor) = 5,15-diphenyl-10-(p-tert-butylphenyl)corrole, Ar = 2,4,6-Me3C6H2 (Mes), 2,6-(iPr)2C6H3 (Dipp), 2,4,6-(iPr)3C6H2 (Tipp), and 3,5-(CF3)2C6H3 (BTF)) can be prepared from [Ru(tBu-Cor)]2 under strongly reducing conditions. This type of Ru(v)-monoarylimido corrole complex with S = ½ was characterized by high-resolution ESI mass spectrometry, X-band EPR, resonance Raman spectroscopy, magnetic susceptibility, and elemental analysis, together with computational studies. Under heating/light irradiation (xenon lamp) conditions, the complexes [Ru(tBu-Cor)(NAr)] (Ar = Mes, BTF) could undergo aziridination of styrenes and amination of benzylic C(sp3)-H bonds with up to 90% product yields.

Multiple reaction pathway on alkaline earth imide supported catalysts for efficient ammonia synthesis.

The tunability of reaction pathways is required for exploring efficient and low cost catalysts for ammonia synthesis. There is an obstacle by the limitations arising from scaling relation for this purpose. Here, we demonstrate that the alkali earth imides (AeNH) combined with transition metal (TM = Fe, Co and Ni) catalysts can overcome this difficulty by utilizing functionalities arising from concerted role of active defects on the support surface and loaded transition metals. These catalysts enable ammonia production through multiple reaction pathways. The reaction rate of Co/SrNH is as high as 1686.7 mmol·gCo-1·h-1 and the TOFs reaches above 500 h-1 at 400 °C and 0.9 MPa, outperforming other reported Co-based catalysts as well as the benchmark Cs-Ru/MgO catalyst and industrial wüstite-based Fe catalyst under the same reaction conditions. Experimental and theoretical results show that the synergistic effect of nitrogen affinity of 3d TMs and in-situ formed NH2- vacancy of alkali earth imides regulate the reaction pathways of the ammonia production, resulting in distinct catalytic performance different from 3d TMs. It was thus demonstrated that the appropriate combination of metal and support is essential for controlling the reaction pathway and realizing highly active and low cost catalysts for ammonia synthesis.

Tailoring the growth route of lithium peroxide through the rational design of a sodium-doped nickel phosphate catalyst for lithium-oxygen batteries.

Tailoring the morphology and structure of Li2O2, the discharge product of lithium-oxygen batteries (LOBs), through the rational design of cathode catalysts is an efficient strategy to promote the electrochemical performance of LOBs. In this work, sodium-doped nickel phosphate nanorods (Na-NiPO NRs) grown on Ni foam (NF) were prepared by the hydrothermal method and subsequent calcination. For the Na-NiPO NRs, the electronic structure could be optimized and abundant void space among the nanorods would provide abundant transport channels. Adopted as the cathodes, the Na-NiPO NRs could facilitate the uniform growth of sea cucumber-like Li2O2 with sufficient Li2O2-electrolyte and Li2O2-catalyst interfaces, significantly promoting the charge process. Therefore, LOBs could deliver a high discharge capacity of 10365.0 mA h g-1 at 100 mA g-1. And a low potential gap of 1.16 V can be achieved at 200 mA g-1 with a capacity of 500 mA h g-1. The proposed strategy demonstrates the role of the morphology and electronic structure of the cathode catalysts in tuning the Li2O2 morphology and provides a novel approach for achieving high-performance LOBs.

Poly(p-phenylenediamine)-Coated Metal-Organic Frameworks for High-Performance Sodium-Ion Batteries: The Balance of Capacity and Stability.

Metal-organic frameworks (MOFs) with well-defined porous structures and highly active frameworks are considered as promising electrode materials for sodium-ion batteries (SIBs). However, the structure pulverization upon sodiation/desodiation impacts on their practical application in SIBs. To address this issue, poly(p-phenylenediamine) (PPA) was uniformly coated onto the surface of MIL-88A, a typical Fe-based MOF through in situ polymerization initiated by the metal ions (Fe3+) of MIL-88A. Used as an anode material for SIBs, the PPA-coated MIL-88A, denoted as PPA@MIL-88A, showed significantly improved electrochemical performance. A reversible capacity as high as 230 mAh g-1 was achieved at 0.2 A g-1 even after 500 cycles. MIL-88A constructed with electrochemically active Fe3+ and fumaric acid ligands guarantees the high specific capacity, while the PPA polymer coating effectively inhibits the pulverization of MIL-88A. This work provides an efficient strategy for improving the structure and cycling stability of MOFs-based electrode materials.

Tailoring the Growth and Morphology of Lithium Peroxide: Nickel Sulfide/Nickel Phosphate Nanotubes with Optimized Electronic Structure for Lithium-Oxygen Batteries.

Heterogeneous crystalline-amorphous structures, with tunable electronic structures and morphology, hold immense promise as catalysts for lithium-oxygen batteries (LOBs). Herein, a nanotube network constructed by crystalline nickel sulfide/amorphous nickel phosphate (NiS/NiPO) heterostructure is prepared on Ni foam through the sulfurization of the precursor generated hydrothermally. Used as cathodes, the NiS/NiPO nanotubes with optimized electronic structure can induce the deposition of the highly porous and interconnected structure of Li2 O2 with rich Li2 O2 -electrolyte interfaces. Abundant active sites can be created on NiS/NiPO through the charge redistribution for the uniform nucleation and growth of Li2 O2 . Moreover, nanotube networks endow cathodes with efficient transport channels and sufficient space for the accommodation of Li2 O2 . A high discharge capacity of 27 003.6 mAh g-1 and a low charge overpotential of 0.58 V at 1000 mAh g-1 can be achieved at 200 mA g-1 . This work provides valuable insight into the unique role of the electronic structure and morphology of catalysts in the formation mechanisms of Li2 O2 and the performances of LOBs.

Comparison of Functional Health Status and Health Related Quality of Life Between Adult Patients With Fontan Procedure and Noncongenital Heart Diseases.

To compare functional health status and Health Related Quality of Life (HRQoL) between Fontan and non-congenital heart disease (CHD) patients in an Asian population. Functional health status and HRQoL (New York Heart Association (NYHA) functional class, Duke Activity Status Index (DASI), HeartQol and EQ-5D-5L) were measured. A total of 65 patients (twenty Fontan patients, mean age 28 ± 5; and 45 age-matched non-CHD patients, mean age 33 ± 5) were recruited. After adjustment for age, gender and ethnicity, there were no significant differences in functional health status and HRQoL between groups. In an Asian population, Fontan patients have similar functional health status and Health Related Quality of Life compared to non-CHD patients.

Hip subluxation in children with spinal cord injury: Incidence and influencing factors.

OBJECTIVE: Hip subluxation is a common complication in children with spinal cord injury. This study aimed to investigate the incidence and influencing factors of hip subluxation and discuss prevention strategies. METHODS: Medical records of children with spinal cord injury were reviewed. The inclusion criteria were as follows: (1) the patient was younger than 18 years old when injured; (2) absence of traumatic or congenital pathological changes of the hip at the time of injury. The migration percentage and acetabular index were selected to evaluate hip stability and acetabulum development. Influencing factors of sex, age, injury duration, severity, level, and spasticity were analyzed. RESULTS: A total of 146 children were enrolled. Twenty-eight children presented with hip subluxation and were significantly younger at the time of injury than those with normal hips (P = 0.002). The incidence of hip subluxation increased with the prolonged injury duration. Injury before age 6, complete injury, and flaccid lower extremities were significant influencing factors (P = 0.003, 0.004, and 0.015, respectively). The risk of hip subluxation decreased by 18% for every year older in injury age (P = 0.031) and decreased by 85% in children with spasticity (P = 0.018) than those without. However, the risk of hip subluxation in children with injury duration longer than 1 year was 7.1 times higher than those with shorter injury duration (P < 0.001). CONCLUSIONS: The incidence of hip subluxation in children with spinal cord injury increased with the injury duration. Younger children had immature hip development. Due to complete injury and flaccid muscle, lack of protection around the hip may lead to subluxation. Follow-up and prevention of hip subluxation need the joint effort of medical staff and families.

Proteomic profiling of longitudinal changes in kidney function among middle-aged and older men and women: the KORA S4/F4/FF4 study.

BACKGROUND: Due to the asymptomatic nature of the early stages, chronic kidney disease (CKD) is usually diagnosed at late stages and lacks targeted therapy, highlighting the need for new biomarkers to better understand its pathophysiology and to be used for early diagnosis and therapeutic targets. Given the close relationship between CKD and cardiovascular disease (CVD), we investigated the associations of 233 CVD- and inflammation-related plasma proteins with kidney function decline and aimed to assess whether the observed associations are causal. METHODS: We included 1140 participants, aged 55-74 years at baseline, from the Cooperative Health Research in the Region of Augsburg (KORA) cohort study, with a median follow-up time of 13.4 years and 2 follow-up visits. We measured 233 plasma proteins using a proximity extension assay at baseline. In the discovery analysis, linear regression models were used to estimate the associations of 233 proteins with the annual rate of change in creatinine-based estimated glomerular filtration rate (eGFRcr). We further investigated the association of eGFRcr-associated proteins with the annual rate of change in cystatin C-based eGFR (eGFRcys) and eGFRcr-based incident CKD. Two-sample Mendelian randomization was used to infer causality. RESULTS: In the fully adjusted model, 66 out of 233 proteins were inversely associated with the annual rate of change in eGFRcr, indicating that higher baseline protein levels were associated with faster eGFRcr decline. Among these 66 proteins, 21 proteins were associated with both the annual rate of change in eGFRcys and incident CKD. Mendelian randomization analyses on these 21 proteins suggest a potential causal association of higher tumor necrosis factor receptor superfamily member 11A (TNFRSF11A) level with eGFR decline. CONCLUSIONS: We reported 21 proteins associated with kidney function decline and incident CKD and provided preliminary evidence suggesting a potential causal association between TNFRSF11A and kidney function decline. Further Mendelian randomization studies are needed to establish a conclusive causal association.