Design Strategies towards Advanced Hydrogen Evolution Reaction Electrocatalysts at Large Current Densities.

Hydrogen (H2), produced by water electrolysis with the electricity from renewable sources, is an ideal energy carrier for achieving a carbon-neutral and sustainable society. Hydrogen evolution reaction (HER) is the cathodic half-reaction of water electrolysis, which requires active and robust electrocatalysts to reduce the energy consumption for H2 generation. Despite numerous electrocatalysts have been reported by the academia for HER, most of them were only tested under relatively small current densities for a short period, which cannot meet the requirements for industrial water electrolysis. To bridge the gap between academia and industry, it is crucial to develop highly active HER electrocatalysts which can operate at large current densities for a long time. In this review, the mechanisms of HER in acidic and alkaline electrolytes are firstly introduced. Then, design strategies towards high-performance large-current-density HER electrocatalysts from five aspects including number of active sites, intrinsic activity of each site, charge transfer, mass transfer, and stability are discussed via featured examples. Finally, our own insights about the challenges and future opportunities in this emerging field are presented.

Mo-X4 (X = O, NH and S)-mediated triphenylene-based two-dimensional carbon-rich conjugate frameworks for an efficient nitrogen reduction reaction.

The electrocatalytic nitrogen reduction reaction (NRR) is a highly competitive approach for the ammonia synthesis to overcome the problems of high energy consumption and air pollution by the traditional Haber-Bosch process. However, the challenges of inert N2 molecule activation and the competitive hydrogen evolution reaction (HER) restrict the real utilization of the NRR. Herein, by means of density functional theory (DFT) calculations, we proposed three two-dimensional carbon-rich conjugate frameworks (2D-CCFs) with hexa-substituted triphenylene organic linkers with a metal atom Mo and functional groups X (X = O, NH, and S), namely Mo3(HOTP)2, Mo3(HITP)2 and Mo3(THT)2, to investigate their NRR performance. Our theoretical calculations reveal that Mo atoms in 2D-CCFs can efficiently capture and activate N2 molecules. Among the three structures, Mo3(HOTP)2 exhibited the most superior performance toward the NRR with a favorable limiting potential of -0.41 V and good selectivity for the HER. Furthermore, the catalytic efficiency of 2D-CCFs can be regulated by changing the atoms X in Mo-X4 motifs, providing a new scenario for the development of highly efficient NRR catalysts.

Curcumin ameliorates pulmonary fibrosis progression by inhibiting the fibrotic process of lung fibroblasts.

The objective of this study was to analyze the effect of curcumin (Cur) on pulmonary fibrosis (PF), so as to provide new clinical evidence for future PF treatment. To achieve these goals, the researchers set up bought human lung fibroblasts MRC-5 as a control group without treatment, a model group for PF cell modeling, and an intervention group for Cur intervention after PF modeling. Cell proliferation capacity and cellular TGF-ß1, α-SMA, Collagen I, Collagen III, Bax, N-cadherin and E-cadherin protein expression were determined. The results show that markedly enhanced cell proliferation capacity and TGF-ß1, α-SMA, Collagen I and Collagen III protein levels were observed in the model group, while the cell activity and fibrosis degree in the intervention group were significantly decreased compared with the model group (P<0.05). In addition, the intervention group exhibited lower N-cadherin and Bax with higher E-cadherin than the model group (P<0.05). In addition, the team found that the inflammatory response and oxidative stress were also more significantly improved in the intervention group (P<0.05). These experimental results tell us that Cur can ameliorate the fibrotic process of PF by inhibiting the activity of MRC-5.

Cu doping in FeP enabling efficient electrochemical nitrate reduction to ammonia in neutral media.

Electrochemical nitrate reduction to ammonia (NH3) not only provides a promising strategy for green NH3 synthesis, but also removes harmful nitrates from water. Herein, a Cu-doped FeP electrocatalyst was prepared for nitrate reduction, which achieved a high NH3 faradaic efficiency of 92.5% and a high NH3 yield of 0.787 mmol h-1 cm-2 in a neutral electrolyte, greatly surpassing its FeP counterpart.

Regulatory effect and mechanism of LncRNA SOX2OT in idiopathic pulmonary fibrosis.

This study discusses the role played by long noncoding RNA (lncRNA) SOX2OT (SOX2OT) in idiopathic pulmonary fibrosis (IPF). By inducing human embryonic lung fibroblasts (MRC5) through hypoxia, the researchers observed changes in SOX2OT expression and fibrotic processes during hypoxia. Moreover, SOX2OT abnormal expression vectors were constructed and transfected into MRC5 to analyze the effect of SOX2OT on MRC5. The results showed that the expression levels of SOX2OT and α-SMA were elevated under hypoxic conditions and were positively correlated (P<0.05). α-SMA, Collagen I and Collagen III protein expression and SOX2OT levels all increased under hypoxia (P<0.05). Finally, silencing SOX2OT expression led to weakened MRC5 proliferation, inhibited fibrosis process, and reduced inflammation (P<0.05). In conclusion, SOX2OT is closely related to the occurrence and development of IPF, and silencing its expression can inhibit fibrosis progression.

Risk factors assessment and a Bayesian network model for predicting ischemic stroke in patients with cardiac myxoma.

Objective: This study aims to identify relevant risk factors, assess the interactions between variables, and establish a predictive model for ischemic stroke (IS) in patients with cardiac myxoma (CM) using the Bayesian network (BN) approach. Methods: Data of patients with CM were collected from three tertiary comprehensive hospitals in Beijing from January 2002 to January 2022. Age, sex, medical history, and information related to CM were extracted from the electronic medical record system. The BN model was constructed using the tabu search algorithm, and the conditional probability of each node was calculated using the maximum likelihood estimation method. The probability of each node of the network and the interrelationship between IS and its related factors were qualitatively and quantitatively analyzed. A receiver operating characteristic (ROC) curve was also plotted. Sensitivity, specificity, and area under the curve (AUC) values were calculated and compared between the BN and logistic regression models to evaluate the efficiency of the predictive model. Results: A total of 416 patients with CM were enrolled in this study, including 61 with and 355 without IS. The BN model found that cardiac symptoms, systemic embolic symptoms, platelet counts, and tumor with high mobility were directly associated with the occurrence of IS in patients with CM. The BN model for predicting CM-IS achieved higher scores on AUC {0.706 [95% confidence interval (CI), 0.639-0.773]} vs. [0.697 (95% CI, 0.629-0.766)] and sensitivity (99.44% vs. 98.87%), but lower scores on accuracies (85.82% vs. 86.06%) and specificity (6.56% vs. 11.48%) than the logistic regression model. Conclusion: Cardiac symptoms, systemic embolic symptoms, platelet counts, and tumor with high mobility are candidate predictors of IS in patients with CM. The BN model was superior or at least non-inferior to the traditional logistic regression model, and hence is potentially useful for early IS detection, diagnosis, and prevention in clinical practice.

Coupling Cu doping and oxygen vacancies in Co3O4 for efficient electrochemical nitrate conversion to ammonia.

Electrochemical conversion of nitrate to NH3 not only eliminates nitrate pollution in the environment, but also produces highly valuable NH3. Herein, Cu-doped Co3O4 with abundant oxygen vacancies (Cu-Co3O4-x) was prepared on carbon cloth. The as-fabricated Cu-Co3O4-x can selectively reduce nitrate to NH3 with high Faraday efficiencies (around 90%) and a large NH3 yield of 0.83 mmol h-1 cm-2 in a neutral electrolyte.

Geometric and Electronic Engineering of Atomically Dispersed Copper-Cobalt Diatomic Sites for Synergistic Promotion of Bifunctional Oxygen Electrocatalysis in Zinc-Air Batteries.

The development of rechargeable zinc-air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional oxygen reduction/evolution reaction (ORR/OER) activities. However, the design of such electrocatalysts with high activity and durability is challenging. Herein, a strategy is proposed to create an electrocatalyst comprised of copper-cobalt diatomic sites on a highly porous nitrogen-doped carbon matrix (Cu-Co/NC) with abundantly accessible metal sites and optimal geometric and electronic structures. Experimental findings and theoretical calculations demonstrate that the synergistic effect of Cu-Co dual-metal sites with metal-N4 coordination induce asymmetric charge distributions with moderate adsorption/desorption behavior with oxygen intermediates. This electrocatalyst exhibits extraordinary bifunctional oxygen electrocatalytic activities in alkaline media, with a half-wave potential of 0.92 V for ORR and a low overpotential of 335 mV at 10 mA cm-2 for OER. In addition, it demonstrates exceptional ORR activity in acidic (0.85 V) and neutral (0.74 V) media. When applied to a zinc-air battery, it achieves extraordinary operational performance and outstanding durability (510 h), ranking it as one of the most efficient bifunctional electrocatalysts reported to date. This work demonstrates the importance of geometric and electronic engineering of isolated dual-metal sites for boosting bifunctional electrocatalytic activity in electrochemical energy devices.

Computational Screening of Two-Dimensional Metal-Organic Frameworks as Efficient Single-Atom Catalysts for Oxygen Reduction Reaction.

The development of efficient and inexpensive oxygen reduction reaction (ORR) catalysts is crucial for renewable energy technologies. Herein, using density functional theory (DFT) methods and microkinetic simulations, we systematically investigated the ORR catalytic performance of a series of 2D metal-organic frameworks M3 (HADQ)2 (HADQ=2,3,6,7,10,11-hexaamine dipyrazino quinoxaline). It shows that all 2D M3 (HADQ)2 (M=Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh and Pd) monolayers are metallic, due to π-conjugated crystal orbitals centered on the central metals and ligand N atoms. The catalytic activity of M3 (HADQ)2 depends on the binding strength between ORR intermediates and metal species, and can be tuned via changing the central metals. Among these candidates, Rh3 (HADQ)2 and Co3 (HADQ)2 show superior ORR performance to Pt (111) with high half-wave potentials of 0.99 and 0.93 V, respectively. Moreover, the screened two catalysts have excellent intermediate-tolerance ability for dynamic coverage of oxygenated species on the active sites. Our work provides a new path towards developing efficient ORR electrocatalysts.

Anti-CD19 CAR T-cell consolidation therapy combined with CD19+ feeding T cells and TKI for Ph+ acute lymphoblastic leukemia.

We conducted a single-arm, open-label, single-center phase 1 study to assess the safety and efficacy of multicycle-sequential anti-CD19 chimeric antigen receptor (CAR) T-cell therapy in combination with autologous CD19+ feeding T cells (FTCs) and tyrosine kinase inhibitor (TKI) as consolidation therapy in patients under the age of 65 years with de novo Ph-positive CD19+ B-cell acute lymphoblastic leukemia. Participants were given induction chemotherapy as well as systemic chemotherapy with TKI. Afterward, they received a single cycle of CD19 CAR T-cell infusion and another 3 cycles of CD19 CAR T-cell and CD19+ FTC infusions, followed by TKI as consolidation therapy. CD19+ FTCs were given at 3 different doses. The phase 1 results of the first 15 patients, including 2 withdrawals, are presented. The most common adverse events were cytopenia (13/13) and hypogammaglobinemia (12/13). There was no incidence of cytokine release syndrome above grade 2 or immune effector cell-associated neurotoxicity syndrome or grade 4 nonhematological toxicities. All 13 patients achieved complete remission, including 12 patients with a complete molecular response (CMR) at the data cutoff. The relapse-free survival was 84%, and the overall survival was 83% with a median follow-up of 27 months. The total number of CD19-expressing cells decreased with an increasing CMR rate. CD19 CAR T cells survived for up to 40 months, whereas CD19+ FTCs vanished in 8 patients 3 months after the last infusion. These findings could form the basis for the development of an allo-HSCT-free consolidation paradigm. This trial was registered at www.clinicaltrials.gov as #NCT03984968.

Self-Supported Ru-Incorporated NiSe2 for Ampere-Level Current Density Hydrogen Evolution.

To meet the requirements for industrial water splitting to generate hydrogen, it is urgent, but still quite challenging to develop highly active and stable electrocatalysts for large-current-density hydrogen evolution reaction (HER). Herein, Ru-incorporated NiSe2 (Ru-NiSe2 ) was designed and synthesized. The introduction of Ru results in the formation of hierarchically structured Ru-NiSe2 with large electrochemical active surface area, and well-modified electronic structure. As expected, the as-fabricated Ru-NiSe2 displays impressive HER activity in 1.0 M KOH, with a low overpotential of 180.8 mV to reach the current density of 1000 mA cm-2 . Ru-NiSe2 also presents outstanding long-term stability at high current densities, owing to its high intrinsic chemical stability, and strong catalyst-support interface. Notably, when performed at a certain current density of 1000 mA cm-2 , the overpotential increase after 90 h is only 13 mV. Such excellent HER performance of Ru-NiSe2 demonstrates its great potential for practical use in industrial water splitting.

Scalable synthesis of CuSn bimetallic catalyst for selective CO2 electroreduction to CO over a wide potential range.

A scalable, and cost-effective method was employed to prepare self-supported CuSn bimetallic catalyst on carbon paper. The obtained CuSn catalyst demonstrates high faradaic efficiency of CO around or above 90% at a broad potential range from -0.7 to -1.8 V vs. reversible hydrogen electrode, greatly surpassing Cu or Sn counterparts.

Clinical features, risk factors and survival in cardiac myxoma-related ischemic stroke: A multicenter case-control study.

BACKGROUND: Cardiac myxoma (CM) is an important etiology of stroke in young adults, but studies on CM-related ischemic stroke (CM-IS) are limited and conflicting. Hence, we investigated clinical characterizations, risk factors of CM-IS, and short-term survival after surgical resection. METHODS: We performed a retrospective analysis of data from all CM patients at three referral management centers and conducted follow-up examination. RESULTS: Among 414 CM patients, 402 were recruited for further analysis, including 54 patients with CM-IS and 348 patients with CM without stroke (Non-stroke). In the acute phase, patients presented with NIHSS 3 (interquartile range: 0-10) and clinical presentation comprising neurological, cardiac and constitutional symptoms. Multivariate analysis showed that the factors associated with an increased risk of CM-IS were tumor width < 30 mm [OR = 2.652, 95% CI: 1.061-6.627, P = 0.037], tumors with high-mobility (OR = 2.700, 95% CI: 1.357-5.371, P = 0.005), thrombus on the tumor surface (OR = 1.856, 95% CI: 1.003-3.434, P = 0.049), and lower B-type natriuretic peptide (BNP) levels (OR = 0.995, 95% CI: 0.989-0.999, P = 0.047). The overall three-year survival rate was 95.7% (95% CI: 94.9-96.5) in CM-IS patients who underwent surgery. CONCLUSIONS: CM-IS patients had mild or moderate neurologic deficits with various presentations at disease onset. Narrower tumor width, tumors with high-mobility, thrombus on the tumor surface, and lower BNP levels are potential predictors of CM-IS development. Surgical removal of CM is safe and efficacious in patients with CM-IS.

[Comparison of Therapeutic Efficacy between Hypomenthylating Agents Combined with Venetoclax and Half Dose Priming Regimen in Elderly Patients with Newly Diagnosed Acute Myeloid Leukemia].

OBJECTIVE: To compare the clinical efficacy and safety of hypomenthylating agents (HMA) combined with Venetoclax (VEN) and half dose priming regimen (CAG-like) in the treatment of elderly patients with newly diagnosed acute myeloid leukemia (AML) who were not suitable for intensive chemotherapy. METHODS: The clinical data of 43 newly diagnosed elderly patients with AML who were not suitable for intensive chemotherapy in our hospital from April 2019 to October 2020 were retrospectively analyzed. Among them, 16 cases received HMA-VEN regimen and 27 cases received HMA-CAG-like regimen. The remission rate, early mortality and survival were compared between the two groups. And, the patients were grouped according to HCT-CI score. The effects of two different regimens in different groups on the efficacy and survival of patients were compared, and the prognosis of patients was further analyzed. RESULTS: After one course of treatment, the total remission rate of HMA-VEN group and HMA-CAG-like group was 81.3% (13/16) and 51.9% (14/27), respectively, and the difference between the two groups was statistically significant (χ2=4.650, P=0.045). The median overall survival (OS) time of HMA-VEN group had not yet reached, while that of HMA-CAG-like group was 11.2 months, and the HMA-VEN group had a longer OS (P=0.055). There was no tumor lysis syndrome occurred in both groups. The main adverse reactions were digestive tract reaction, bone marrow suppression and infection. The amount of agranulocytosis infection, pulmonary infection and platelet infusion in HMA-VEN group were significantly lower than those in HMA-CAG-like group (P<0.05), while the time of agranulocytosis and amount of erythrocyte infusion were similar (P>0.05). In HMA-Ven group 1 case died early, while in HMA-CAG-like group 8 cases died early due to pulmonary infection, respiratory failure, cerebral hemorrhage, and alveolar hemorrhage, the mortality in HMA-CAG-like group was significantly higher than that in HMA-VEN group (P=0.043). Among 43 patients, there was a significant difference in OS between HCT score 0-2 group and ≥3 group (P=0.033). In HMA-CAG-like group, patients with HCT score ≥3 had a worse prognosis (P=0.01), while in HMA-VEN group patients showed no statistically significant difference in prognosis (P=0.681). In HCT score 0-2 group, 9 cases receiving HMA-VEN regimen and 22 cases receiving HMA-CAG-like regimen showed no statistical difference in OS (P=0.281). In HCT score ≥3 group, 7 cases receiving HMA-VEN regimen had a longer OS than 5 cases receiving HMA-CAG-like regimen (P=0.015). CONCLUSION: Venetoclax combined with HMA can achieve higher response rate, lower early mortality, and longer OS, especially in those with more comorbidities and poor tolerability.

Acetate promotes the formation of NiRu/NiO towards efficient hydrogen evolution.

The introduction of acetate in the precursor of metal-organic frameworks (MOFs) turns the final product from MOFs to NiRu/Ni(OH)2. Followed by annealing treatment, the obtained NiRu/NiO catalyst exhibits high hydrogen evolution reaction (HER) activity with a low overpotential (18 mV at 10 mA cm-2), and a small Tafel slope of 43.3 mV dec-1 in alkaline electrolyte.

Detection and Significance of Cell-Free DNA Mutation in Pleural Effusion in Patients with Advanced NSCLC.

Objective: To detect EGFR/KRAS genes in pleural effusion cell-free DNA in patients with advanced non-small-cell lung cancer (NSCLC) and to explore the clinical significance of EGFR/KRAS mutation status in pleural effusion. Methods: A retrospective collection was performed on the specimens of pleural effusion and matched tissues from 50 patients with advanced NSCLC admitted to the hospital between January 2019 and January 2021. DNA mutation status of EGFR/KRAS in different specimens was detected and compared by pyrosequencing. The clinicopathological data and follow-up data of survival were collected. The relationship between DNA mutation and clinicopathological characteristics and prognosis was analyzed. Results: In the 50 pleural effusion specimens, there were 22 cases (44.00%) with EGFR mutations (19/21 exon mutations), including 12 cases with EGFR19 deletion mutation and 10 cases with EGFR21 exon L858R mutation. There were 6 cases (12.00%) with KRAS mutations (single-base substitution mutations), including 4 cases with 12-codon mutation and 2 cases with 13-codon mutation. In the 50 tissue specimens, there were 24 cases (48.00%) with EGFR mutations and 4 cases (8.00%) with KRAS mutations. There was no significant difference between pleural effusion specimens and tissue specimens, with good consistency (kappa = 0.920-0.779, P > 0.05). EGFR mutation in pleural effusion was related to smoking history, types of pathological tissues, and lymph node metastasis (P < 0.05). The incidence of EGFR mutation was higher in nonsmokers, patients with lung adenocarcinoma, and patients with lymph node metastasis. The carcinoembryonic antigen (CEA) in patients with EGFR mutation was higher than that with wild-type EGFR, while the level of cytokeratin 19 fragment (Cy21-1) was lower than that with wild-type EGFR (P < 0.05). The 1-year overall survival rate in the EGFR mutation group was significantly higher than that in the EGFR wild group (68.18% vs. 42.86%) (HR = 0.419, 95% CI = 0.178-0.989, and P < 0.001). Conclusion: For the detection of EGFR gene mutation, the results of the pleural effusion specimens and the tumor pathological tissue specimens were well consistent and the detection of pleural effusion could be used as an alternative method when tissue specimens cannot be obtained. EGFR gene mutations are present in majority in patients with advanced NSCLC. The incidence of EGFR mutation is higher in nonsmokers, patients with lung adenocarcinoma, those with lymph node metastasis, those with high-expression CEA, and those with low-expression Cy21-1. The prognosis is better in patients with EGFR mutation.

Phosphate ion functionalized CoP nanowire arrays for efficient alkaline hydrogen evolution.

It is revealed that phosphate ion functionalization of transition metal phosphides can achieve outstanding alkaline hydrogen evolution performance. Herein, the obtained phosphate ion functionalized CoP nanowire arrays exhibit high hydrogen evolution reaction (HER) activity (an overpotential of 112 mV to afford 100 mA cm-2), a low Tafel slope (49 mV dec-1) and outstanding stability in 1.0 M KOH.

In Situ Exfoliation and Pt Deposition of Antimonene for Formic Acid Oxidation via a Predominant Dehydrogenation Pathway.

Direct formic acid fuel cell (DFAFC) has been considered as a promising energy conversion device for stationary and mobile applications. Advanced platinum (Pt) electrocatalysts for formic acid oxidation reaction (FAOR) are critical for DFAFC. However, the oxidation of formic acid on Pt catalysts often occurs via a dual pathway mechanism, which hinders the catalytic activity owing to the CO poisoning. Herein, we directly exfoliate bulk antimony to 2D antimonene (Sb) and in situ load Pt nanoparticles onto antimonene sheets with the assistance of ethylenediamine. According to the Bader charge analysis, the charge transfer from antimonene to Pt occurs, confirming the electronic interaction between Pt and Sb. Interestingly, antimonene, as a cocatalyst, alters the oxidation pathway for FAOR over Pt catalyst and makes FAOR follow the more efficient dehydrogenation pathway. The density functional theory (DFT) calculation demonstrates that antimonene can activate Pt to be a lower oxidative state and facilitate the oxidation of HCOOH into CO2 via a direct pathway, resulting in a weakened intermediate binding strength and better CO tolerance for FAOR. The specific activity of FAOR on Pt/Sb is 4.5 times, and the mass activity is 2.6 times higher than the conventional Pt/C.