Computational chemistry for water-splitting electrocatalysis.

Electrocatalytic water splitting driven by renewable electricity has attracted great interest in recent years for producing hydrogen with high-purity. However, the practical applications of this technology are limited by the development of electrocatalysts with high activity, low cost, and long durability. In the search for new electrocatalysts, computational chemistry has made outstanding contributions by providing fundamental laws that govern the electron behavior and enabling predictions of electrocatalyst performance. This review delves into theoretical studies on electrochemical water-splitting processes. Firstly, we introduce the fundamentals of electrochemical water electrolysis and subsequently discuss the current advancements in computational methods and models for electrocatalytic water splitting. Additionally, a comprehensive overview of benchmark descriptors is provided to aid in understanding intrinsic catalytic performance for water-splitting electrocatalysts. Finally, we critically evaluate the remaining challenges within this field.

γ-MnO2 as an Electron Reservoir for RuO2 Oxygen Evolution Catalyst in Acidic Media.

Developing highly active and durable catalysts in acid conditions remains an urgent issue due to the sluggish kinetics of oxygen evolution reaction (OER). Although RuO2 has been a state-of-the-art commercial catalyst for OER, it encounters poor stability and high cost. In this study, the electronic reservoir regulation strategy is proposed to promote the performance of acidic water oxidation via constructing a RuO2/MnO2 heterostructure supported on carbon cloth (CC) (abbreviated as RuO2/MnO2/CC). Theoretical and experimental results reveal that MnO2 acts as an electron reservoir for RuO2. It facilitates electron transfer from RuO2, enhancing its activity prior to OER, and donates electrons to RuO2, improving its stability after OER. Consequently, RuO2/MnO2/CC exhibits better performance compared to commercial RuO2, with an ultrasmall overpotential of 189 mV at 10 mA cm-2 and no signs of deactivation even after 800 h of electrolysis in 0.5 m H2SO4 at 10 mA cm-2. When applied as the anode in a proton exchange membrane water electrolyzer, the cost-efficient RuO2/MnO2/CC catalyst only requires a cell voltage of 1.661 V to achieve the water-splitting current of 1 A cm-2, and the noble metal cost is as low as US$ 0.00962 cm-2, indicating potential for practical applications.

Regulating Hydrogen/Oxygen Species Adsorption via Built-in Electric Field -Driven Electron Transfer Behavior at the Heterointerface for Efficient Water Splitting.

Alkaline water electrolysis (AWE) plays a crucial role in the realization of a hydrogen economy. The design and development of efficient and stable bifunctional catalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are pivotal to achieving high-efficiency AWE. Herein, WC1-x/Mo2C nanoparticle-embedded carbon nanofiber (WC1-x/Mo2C@CNF) with abundant interfaces is successfully designed and synthesized. Benefiting from the electron transfer behavior from Mo2C to WC1-x, the electrocatalysts of WC1-x/Mo2C@CNF exhibit superior HER and OER performance. Furthermore, when employed as anode and cathode in membrane electrode assembly devices, the WC1-x/Mo2C@CNF catalyst exhibits enhanced catalytic activity and remarkable stability for 100 hours at a high current density of 200 mA cm-2 towards overall water splitting. The experimental characterizations and theoretical simulation reveal that modulation of the d-band center for WC1-x/Mo2C@CNF, achieved through the asymmetric charge distribution resulting from the built-in electric field induced by work function, enables optimization of adsorption strength for hydrogen/oxygen intermediates, thereby promoting the catalytic kinetics for overall water splitting. This work provides promising strategies for designing highly active catalysts in energy conversion fields.

General Approach to Construct C-C Single Bond-Linked Covalent Organic Frameworks.

C-C single bond-linked covalent organic frameworks (CSBL-COFs) are extremely needed because of their excellent stabilities and potential applications in harsh conditions. However, strategies to generate CSBL-COFs are limited to the acetylenic self-homocoupling Glaser-Hay reaction or post-synthetic reduction of vinylene-based COFs. Exploring new strategies to expand the realm of CSBL-COFs is urgently needed but extremely challenging. To address the synthetic challenges, we for the first time developed a general approach via the reaction between aromatic aldehydes and active methyl group-involving monomers with enhanced acidity, which realized the successful construction of a series of CSBL-COFs. As expected, the obtained CSBL-COFs exhibited outstanding chemical stability, which can stabilize in 6 M NaOH, 3 M HCl, boiling water, and 100 mg/mL NaBH4 for at least 3 days. It is important to mention that CSBL-COFs possess a large amount of ionic sites distributed throughout the networks; gentle shaking allowed our COFs to easily self-disperse as nanoparticles and suspend in water for at least 12 h without reprecipitating. As far as we know, such self-dispersed COFs with high water dispersity are rare to date, and few examples are mainly limited to the guanidinium- and pseudorotaxane-based COFs. Our work thus developed a family of self-dispersed COFs for potential applications in different sorts of fields. Our contribution would thus pave a new avenue for constructing a broader class of CSBL-COFs for their wide applications in various fields.

A case report of Klebsiella aerogenes-caused lumbar spine infection identified by metagenome next-generation sequencing.

BACKGROUND: The early clinical diagnosis of spinal infections in elderly patients with recessive or atypical symptoms is difficult. Klebsiella aerogenes is a common opportunistic bacterium that can infect the respiratory tract, urinary tract, and even the central nervous system. However, whether it can infect the lumbar spine has not been previously described. CASE PRESENTATION: In this paper, we report the case of a 69-year-old female patient with osteoporosis who was initially diagnosed with hemolytic anemia. Later, she was diagnosed with K. aerogenes infection of the lumbar spine based on imaging combined with blood culture and metagenome next-generation sequencing (mNGS) detection. After precise medication, the lumbar degeneration was improved. CONCLUSIONS: Bacterial infection should therefore be considered in cases of lumbar degenerative disease in middle-aged and elderly patients.

Progress in Hydrogen Production Coupled with Electrochemical Oxidation of Small Molecules.

The electrochemical oxidation of small molecules to generate value-added products has gained enormous interest in recent years because of the advantages of benign operation conditions, high conversion efficiency and selectivity, the absence of external oxidizing agents, and eco-friendliness. Coupling the electrochemical oxidation of small molecules to replace oxygen evolution reaction (OER) at the anode and the hydrogen evolution reaction (HER) at the cathode in an electrolyzer would simultaneously realize the generation of high-value chemicals or pollutant degradation and the highly efficient production of hydrogen. This Minireview presents an introduction on small-molecule choice and design strategies of electrocatalysts as well as recent breakthroughs achieved in the highly efficient production of hydrogen. Finally, challenges and future orientations are highlighted.

MOFs-Derived Carbon-Based Metal Catalysts for Energy-Related Electrocatalysis.

Electrochemical devices, as renewable and clean energy systems, display a great potential to meet the sustainable development in the future. However, well-designed and highly efficient electrocatalysts are the technological dilemmas that retard their practical applications. Metal-organic frameworks (MOFs) derived electrocatalysts exhibit tunable structure and intriguing activity and have received intensive investigation in recent years. In this review, the recent progress of MOFs-derived carbon-based single atoms (SAs) and metal nanoparticles (NPs) catalysts for energy-related electrocatalysis is summarized. The effects of synthesis strategy, coordination environment, morphology, and composition on the catalytic activity are highlighted. Furthermore, these SAs and metal NPs catalysts for the applications of electrocatalysis (hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction) are overviewed. Finally, some current challenges and foresighted ideas for MOFs-derived carbon-based metal electrocatalysts are presented.

P-Block Atomically Dispersed Antimony Catalyst for Highly Efficient Oxygen Reduction Reaction.

Main-group (s- and p-block) metals are generally regarded as catalytically inactive due to the delocalized s/p-band. Herein, we successfully synthesized a p-block antimony single-atom catalyst (Sb SAC) with the Sb-N4 configuration for efficient catalysis of the oxygen reduction reaction (ORR). The obtained Sb SAC exhibits superior ORR activity with a half-wave potential of 0.86 V and excellent stability, which outperforms most transition-metal (TM, d-block) based SACs and commercial Pt/C. In addition, it presents an excellent power density of 184.6 mW cm-2 and a high specific capacity (803.5 mAh g-1 ) in Zn-air battery. Both experiment and theoretical calculation manifest that the active catalytic sites are positively charged Sb-N4 single-metal sites, which have closed d shells. Density of states (DOS) results unveil the p orbital of the atomically dispersed Sb cation in Sb SAC can easily interact with O2 -p orbital to form hybrid states, facilitating the charge transfer and generating appropriate adsorption strength for oxygen intermediates, lowering the energy barrier and modulating the rate-determining step. This work sheds light on the atomic-level preparing p-block Sb metal catalyst for highly active ORR, and further provides valuable guidelines for the rational design of other main-group-metal SACs.

Gemella morbillorum infective endocarditis: A case report and literature review.

Infective endocarditis (IE) caused by Gemella morbillorum is rare. Consequently, little is known about the natural course of endocarditis caused by this pathogen. This report describes the case of a 37-year-old male patient with G. morbillorum endocarditis. The patient was hospitalized for a fever of unknown origin. He complained of intermittent fever of unknown origin for 2 months. He had also undergone root canal therapy for pulpitis a month ago. After admission, the infectious pathogen G. morbillorum was identified using metagenomic next-generation sequence technology. The anaerobic blood culture bottle showed only Gram-positive cocci. Transthoracic echocardiography showed 10 mm vegetation on the aorta, which met the IE diagnostic Duke's criteria, and the patient was diagnosed with G. morbillorum IE. Because no bacterial colonies were formed on the culture, the drug sensitivity test could not be conducted. Ceftriaxone anti-infective drugs are based on careful consideration of the literature and patient. Six days after antibiotic treatment in our department, the patient was discharged from the hospital in stable condition and had no adverse reactions at 1 week of follow-up. To help clinicians better understand the disease of G. morbillorum IE, we also reviewed and discussed the relevant cases published after 2010 when presenting the report.

Vascular Stem/Progenitor Cells in Vessel Injury and Repair.

Vascular repair upon vessel injury is essential for the maintenance of arterial homeostasis and function. Stem/progenitor cells were demonstrated to play a crucial role in regeneration and replenishment of damaged vascular cells during vascular repair. Previous studies revealed that myeloid stem/progenitor cells were the main sources of tissue regeneration after vascular injury. However, accumulating evidences from developing lineage tracing studies indicate that various populations of vessel-resident stem/progenitor cells play specific roles in different process of vessel injury and repair. In response to shear stress, inflammation, or other risk factors-induced vascular injury, these vascular stem/progenitor cells can be activated and consequently differentiate into different types of vascular wall cells to participate in vascular repair. In this review, mechanisms that contribute to stem/progenitor cell differentiation and vascular repair are described. Targeting these mechanisms has potential to improve outcome of diseases that are characterized by vascular injury, such as atherosclerosis, hypertension, restenosis, and aortic aneurysm/dissection. Future studies on potential stem cell-based therapy are also highlighted.

Metagenomic Assessment of the Pathogenic Risk of Microorganisms in Sputum of Postoperative Patients With Pulmonary Infection.

Respiratory infections are complicated biological processes associated with an unbalanced microbial community and a wide range of pathogens. To date, robust approaches are still required for distinguishing the pathogenic microorganisms from the colonizing ones in the clinical specimens with complex infection. In this study, we retrospectively analyzed the data of conventional culture testing and metagenomic next-generation sequencing (mNGS) of the sputum samples collected from 50 pulmonary infected patients after cardiac surgery from December 2020 and June 2021 in Ruijin Hospital. Taxonomic classification of the sputum metagenomes showed that the numbers of species belonging to bacteria, fungi, and viruses were 682, 58, and 21, respectively. The full spectrum of microorganisms present in the sputum microbiome covered all the species identified by culture, including 12 bacterial species and two fungal species. Based on species-level microbiome profiling, a reference catalog of microbial abundance detection limits was constructed to assess the pathogenic risks of individual microorganisms in the specimens. The proposed screening procedure detected 64 bacterial pathogens, 10 fungal pathogens, and three viruses. In particular, certain opportunistic pathogenic strains can be distinguished from the colonizing ones in the individual specimens. Strain-level identification and phylogenetic analysis were further performed to decipher molecular epidemiological characteristics of four opportunistic etiologic agents, including Klebsiella pneumoniae, Corynebacterium striatum, Staphylococcus aureus, and Candida albicans. Our findings provide a novel metagenomic insight into precision diagnosis for clinically relevant microbes, especially for opportunistic pathogens in the clinical setting.

N-doped ZrO2 nanoparticles embedded in a N-doped carbon matrix as a highly active and durable electrocatalyst for oxygen reduction.

Fabricating highly efficient and robust oxygen reduction reaction (ORR) electrocatalysts is challenging but desirable for practical Zn-air batteries. As an early transition-metal oxide, zirconium dioxide (ZrO2) has emerged as an interesting catalyst owing to its unique characteristics of high stability, anti-toxicity, good catalytic activity, and small oxygen adsorption enthalpies. However, its intrinsically poor electrical conductivity makes it difficult to serve as an ORR electrocatalyst. Herein, we report ultrafine N-doped ZrO2 nanoparticles embedded in an N-doped porous carbon matrix as an ORR electrocatalyst (N-ZrO2/NC). The N-ZrO2/NC catalyst displays excellent activity and long-term durability with a half-wave potential (E1/2) of 0.84 V and a selectivity for the four-electron reduction of oxygen in 0.1 M KOH. Upon employment in a Zn-air battery, N-ZrO2/NC presented an intriguing power density of 185.9 mW cm-2 and a high specific capacity of 797.9 mA h gZn -1, exceeding those of commercial Pt/C (122.1 mW cm-2 and 782.5 mA h gZn -1). This excellent performance is mainly attributed to the ultrafine ZrO2 nanoparticles, the conductive carbon substrate, and the modified electronic band structure of ZrO2 after N-doping. Density functional theory calculations demonstrated that N-doping can reduce the band-gap of ZrO2 from 3.96 eV to 3.33 eV through the hybridization of the p state of the N atom with the 2p state of the oxygen atom; this provides enhanced electrical conductivity and results in faster electron-transfer kinetics. This work provides a new approach for the design of other enhanced semiconductor and insulator materials.

Infectious native valve endocarditis by Streptococcus agalactiae species: Case report of pathogen identification only through metagenomic sequencing technology.

INTRODUCTION: Streptococcus agalactiae is a common pathogen in infective endocarditis, but the positive rate of traditional blood culture diagnosis is not high. It is challenging to obtain a good outcome in the absence of pathogen information for patients with infectious endocarditis. PATIENT CONCERNS AND DIAGNOSIS: Here, we report the case of a patient with infective endocarditis caused by S. agalactiae. The initial manifestations of this patient were coma, urinary incontinence, and fecal incontinence and had no history of heart disease or infectious diseases before admission. INTERVENTIONS AND OUTCOMES: When the blood culture was negative 3 consecutive times, the pathogen S. agalactiae was diagnosed in a timely and accurate manner by metagenome sequencing. Eventually, the patient was discharged following surgery and antibiotic treatment. CONCLUSIONS: For IE patients with infective endocarditis, metagenome sequencing is a valuable and selective tool for rapid, sensitive, and accurate pathogen detection, especially when the blood culture is negative.

The role of hypoxia-inducible factors in cardiovascular diseases.

Cardiovascular diseases are the leading cause of death worldwide. During the development of cardiovascular diseases, hypoxia plays a crucial role. Hypoxia-inducible factors (HIFs) are the key transcription factors for adaptive hypoxic responses, which orchestrate the transcription of numerous genes involved in angiogenesis, erythropoiesis, glycolytic metabolism, inflammation, and so on. Recent studies have dissected the precise role of cell-specific HIFs in the pathogenesis of hypertension, atherosclerosis, aortic aneurysms, pulmonary arterial hypertension, and heart failure using tissue-specific HIF-knockout or -overexpressing animal models. More importantly, several compounds developed as HIF inhibitors or activators have been in clinical trials for the treatment of renal cancer or anemia; however, little is known on the therapeutic potential of these inhibitors for cardiovascular diseases. The purpose of this review is to summarize the recent advances on HIFs in the pathogenesis and pathophysiology of cardiovascular diseases and to provide evidence of potential clinical therapeutic targets.

Clinical metagenomic sequencing for rapid diagnosis of neonatal meningitis caused by Ureaplasma parvum: A case report.

INTRODUCTION: It is challenging to obtain favorable results through conventional diagnostic testing for Ureaplasma parvum (UP), a conditional pathogen, because of the atypical clinical phenotype of UP meningitis. PATIENT CONCERNS AND DIAGNOSIS: Herein, we report a pediatric case of neonatal meningitis caused by UP in a spontaneously delivered full-term baby. The infant's temperature peak was 38.3°C at the age of 9 days. The patient was diagnosed with neonatal suppurative meningitis. INTERVENTIONS AND OUTCOMES: The pathogen was diagnosed in a timely and accurate manner by metagenome sequencing, and the patient was eventually discharged with azithromycin. CONCLUSIONS: Neonatal Ureaplasma meningitis may be more common than previously suspected. The clinical manifestations were not obvious and were similar to those of neonatal meningitis caused by other bacteria. When conventional treatments and conventional pathogenic tests are negative, mNGS is a better choice for timely and accurate pathogen identification.

Evaluation of the metagenomic next-generation sequencing performance in pathogenic detection in patients with spinal infection.

Spinal infection is a rarely occurred pathology, whose diagnosis remains a major challenge due to the low sensitivity of culturing techniques. Metagenomic next-generation sequencing (mNGS) is a novel approach to identify the pathogenic organisms in infectious diseases. In this study, mNGS technology was adopted for pathogenic detection in spinal infection from the tissue and pus samples. Additionally, the diagnostic performance of mNGS for spinal infection was evaluated, by comparing it with that of the conventional microbial culture, with the histopathological results as the gold standard. Overall, 56 samples from 38 patients were enrolled for mNGS testing, and 69 samples were included for microbial culture. 30 patients (78.95%) were identified to be positive by the mNGS method, which was higher than that of microbial culture (17, 44.74%). The sensitivity and specificity of mNGS with pus samples were 84.2% and 100.0%, respectively, which outperformed those of microbial culture (42.1% and 100.0%). The pathogen identification results were applied to medication guidance, and all 38 patients experienced favorable outcomes at three months, followed-up post-treatment, without any adverse effects. These findings proved that mNGS was superior to microbial culture in pathogenic identification of the spinal infection, thereby showing great promise in guiding drug administration and improving clinical outcomes.