Monosymmetric Fe-N4 sites enabling durable proton exchange membrane fuel cell cathode by chemical vapor modification.

The limited durability of metal-nitrogen-carbon electrocatalysts severely restricts their applicability for the oxygen reduction reaction in proton exchange membrane fuel cells. In this study, we employ the chemical vapor modification method to alter the configuration of active sites from FeN4 to the stable monosymmetric FeN2+N'2, along with enhancing the degree of graphitization in the carbon substrate. This improvement effectively addresses the challenges associated with Fe active center leaching caused by N-group protonation and free radicals attack due to the 2-electron oxygen reduction reaction. The electrocatalyst with neoteric active site exhibited excellent durability. During accelerated aging test, the electrocatalyst exhibited negligible decline in its half-wave potential even after undergoing 200,000 potential cycles. Furthermore, when subjected to operational conditions representative of fuel cell systems, the electrocatalyst displayed remarkable durability, sustaining stable performance for a duration exceeding 248 h. The significant improvement in durability provides highly valuable insights for the practical application of metal-nitrogen-carbon electrocatalysts.

Development and validation of a deep learning model for predicting postoperative survival of patients with gastric cancer.

BACKGROUND: Deep learning (DL), a specialized form of machine learning (ML), is valuable for forecasting survival in various diseases. Its clinical applicability in real-world patients with gastric cancer (GC) has yet to be extensively validated. METHODS: A combined cohort of 11,414 GC patients from the Surveillance, Epidemiology and End Results (SEER) database and 2,846 patients from a Chinese dataset were utilized. The internal validation of different algorithms, including DL model, traditional ML models, and American Joint Committee on Cancer (AJCC) stage model, was conducted by training and testing sets on the SEER database, followed by external validation on the Chinese dataset. The performance of the algorithms was assessed using the area under the receiver operating characteristic curve, decision curve, and calibration curve. RESULTS: DL model demonstrated superior performance in terms of the area under the curve (AUC) at 1, 3, and, 5 years post-surgery across both datasets, surpassing other ML models and AJCC stage model, with AUCs of 0.77, 0.80, and 0.82 in the SEER dataset and 0.77, 0.76, and 0.75 in the Chinese dataset, respectively. Furthermore, decision curve analysis revealed that the DL model yielded greater net gains at 3 years than other ML models and AJCC stage model, and calibration plots at 3 years indicated a favorable level of consistency between the ML and actual observations during external validation. CONCLUSIONS: DL-based model was established to accurately predict the survival rate of postoperative patients with GC.

Single atom sites as CO scavenger to allow for crude hydrogen usage in PEMFC.

Nanosized Pt catalysts are the catalyst-of-choice for proton exchange membrane fuel cell (PEMFC) anode, but are limited by their extreme sensitivity to CO in parts per million (ppm) level, thereby making the use of ultrapure H2 a prerequisite to ensure acceptable performance. Herein, we confront the CO poisoning issue by bringing the Ir/Rh single atom sites to synergistically working with their metallic counterparts. In presence of 1000 ppm CO, the catalyst represents not only undisturbed H2 oxidation reaction (HOR) catalytic behavior in electrochemical cell, but also unparalleled peak power density at 643 mW cm-2 in single cell, 27-fold in mass activity of the best PtRu/C catalysts available. Pre-poisoning experiments and surface-enhanced Raman scattering spectroscopy (SERS) and calculation results in combine suggest the presence of adjacent Ir/Rh single atom sites (SASs) to the nanoparticles (NPs) as the origin for this prominent catalytic behavior. The single sites not only exhibit superb CO oxidation performance by themselves, but can also scavenge the CO adsorbed on approximated NPs via supplying reactive OH* species. We open up a new route here to conquer the formidable CO poisoning issue through single atom and nanoparticle synergistic catalysis, and pave the way towards a more robust PEMFC future.

Depth estimation for broadband sources with a vertical line array in deep water.

In deep water, deploying a short vertical line array (VLA) is an effective way for source localization. In the past decade, most studies focused on localizing sources at the short to moderate ranges in the reliable acoustic path or the direct arrival zone (DAZ), with a VLA deployed near the ocean bottom. Little work has been done for the end part of the DAZ and the zones outside the DAZ. In addition, a VLA deployed at other depths rather than near the bottom is rarely studied. This paper proposes a near-surface source depth estimation method by matching the measured time delay with a library of modeled values under different source depths calculated by a simple formula. This method is suitable for zones, which contains two paths (one is reflected from the sea surface) with very close arrival angles, of a VLA deployed not only near the bottom, but also at other depths of the water column. Source depth estimation strategy for the end part of each zone, which faces the problem of poor depth resolution, is also analyzed. Simulation and experimental data of the airgun and explosive sources in the South China Sea are used to demonstrate the method.

F Doping-Induced Multicomponent Synergistic Active Site Construction toward High-Efficiency Bifunctional Oxygen Electrocatalysis for Rechargeable Zn-Air Batteries.

The commercialization of rechargeable Zn-air batteries (ZABs) relies on the material innovation to accelerate the sluggish oxygen electrocatalysis kinetics. Due to the differentiated mechanisms of reverse processes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), rationally integrating dual sites for bifunctional oxygen electrocatalysis is prerequisite yet remains challenging. Herein, multicomponent synergistic active sites within highly graphitic carbon substrate are exquisitely constructed, which is accomplished by fluorine (F) modulation strategy. The incorporation of F dopants facilitates pyridinic N formation for anchoring single metal sites, thus guaranteeing the coexistence of sufficient M-Nx sites and metal nanoparticles toward bifunctional oxygen electrocatalysis. As a result, the optimal catalyst, denoted as F NH2 -FeNi-800, outperforms commercial Pt/C+RuO2 with smaller gap between Ej = 10 and E1/2 (ΔE) of 0.63 V (vs 0.7 V for Pt/C+RuO2 ), demonstrating its superior bifunctionality. Beyond that, its superiority is validated in homemade rechargeable ZABs. ZABs assembled using F NH2 -FeNi-800 as the air cathode delivers higher peak power density (123.8 mW cm-2 ) and long-cycle lifetime (over 660 cycles) in comparison with Pt/C@RuO2 (68.8 mW cm-2 ; 300 cycles). The finding not only affords a highly promising oxygen electrocatalyst, but also opens an avenue to constructing multifunctional active sites for heterogeneous catalysts.

Rare Earth Evoked Subsurface Oxygen Species in Platinum Alloy Catalysts Enable Durable Fuel Cells.

Alleviating the degradation issue of Pt based alloy catalysts, thereby simultaneously achieving high mass activity and high durability in proton exchange membrane fuel cells (PEMFCs), is highly challenging. Herein, we provide a new paradigm to address this issue via delaying the place exchange between adsorbed oxygen species and surface Pt atoms, thereby inhibiting Pt dissolution, through introducing rare earth bonded subsurface oxygen atoms. We have succeeded in introducing Gd-O dipoles into Pt3 Ni via a high temperature entropy-driven process, with direct spectral evidence attained from both soft and hard X-ray absorption spectroscopies. The higher rated power of 0.93 W cm-2 and superior current density of 562.2 mA cm-2 at 0.8 V than DOE target for heavy-duty vehicles in H2 -air mode suggest the great potential of Gd-O-Pt3 Ni towards practical application in heavy-duty transportation. Moreover, the mass activity retention (1.04 A mgPt -1 ) after 40 k cycles accelerated durability tests is even 2.4 times of the initial mass activity goal for DOE 2025 (0.44 A mgPt -1 ), due to the weakened Pt-Oads bond interaction and the delayed place exchange process, via repulsive forces between surface O atoms and those in the sublayer. This work addresses the critical roadblocks to the widespread adoption of PEMFCs.

Performance comparison of conventional and striation-based beamformers for underwater bearing detection of pulse sources.

The multi-path and dispersion properties of shallow water waveguides make conventional beamforming (CBF) face issues such as beam shift, broadening, splitting, output distortion, and array gain reduction. In this paper, the striation-based beamforming (SBF) is investigated to address these issues. SBF differs from CBF by utilizing frequency-shift processing along interference striations. The performance difference between CBF and SBF is compared. It demonstrates that under ideal waveguide modeling with pulse sources, SBF can achieve a beam output response that is close to the plane wave condition. The speed term of SBF's response is approximately independent of modal indexes, which equips SBF to form a unique beam output and guarantee the beam resolution. The processing of consistent signals along the striation maintains the optimal signal correlation, which makes SBF ensure the output fidelity and array gain. To shift the mainlobe of SBF to the source azimuth, the time delay related to the waveform truncation point can be introduced to pre-compensate the array signals. There exist two theoretical accuracy limits to using the truncation. First, truncation time corresponds to the waveform point at r0/c (r0 is the source range), and the mainlobe of SBF is directed to the source azimuth. Second, truncation corresponds to the pulse peak point, and the azimuth estimation accuracy of SBF gets close to CBF. Simulations and experimental results are given as illustrations.

Sources depth estimation for a tonal source by matching the interference structure in the arrival angle domain.

A publication by McCargar and Zurk [J. Acoust. Soc. Am. 133(4), EL320-EL325 (2013)] introduced a passive source depth estimation method for a moving tonal source with a vertical line array (VLA), utilizing the depth-dependent modulation in the arrival angle domain caused by the interference between the direct and surface-reflected acoustic arrivals. Under the isovelocity approximation, this method can estimate the depth of sources at close ranges, but the depth estimation error will increase with the increase in source range, as the impact of the sound speed profile on sound propagation is ignored. This paper presents a theoretical formula for calculating the modeled interference structure in the arrival angle domain with the knowledge of the sound speed profile. By matching the measured interference structure obtained from the beamforming of the acoustic data received by the VLA with the modeled structure under different assumed source depths, the tonal source depth estimation is achieved, even for sources at the remote part of the direct arrival zone. The performance of this method is verified by simulation data, as well as experimental data radiated from a towed source and a non-cooperative passing ship.

Intrinsic spin shielding effect in platinum-rare-earth alloy boosts oxygen reduction activity.

Oxygen reduction reactions (ORRs) involve a multistep proton-coupled electron process accompanied by the conversion of the apodictic spin configuration. Understanding the role of spin configurations of metals in the adsorption and desorption of oxygen intermediates during ORRs is critical for the design of efficient ORR catalysts. Herein, a platinum-rare-earth-metal-based alloy catalyst, Pt2Gd, is introduced to reveal the role of spin configurations in the catalytic activity of materials. The catalyst exhibits a unique intrinsic spin reconfiguration because of interactions between the Gd-4f and Pt-5d orbitals. The adsorption and desorption of the oxygen species are optimized by modifying the spin symmetry and electronic structures of the material for increased ORR efficiency. The Pt2Gd alloy exhibits a half-wave potential of 0.95 V and a superior mass activity of 1.5 A·mgPt-1 in a 0.1 M HClO4 electrolyte, as well as higher durability than conventional Pt/C catalysts. Theoretical calculations have proven that the spin shielding effect of Gd pairs increases the spin symmetry of Pt-5d orbitals and adsorption preferences toward spin-polarized intermediates to facilitate ORR. This work clarifies the impact of modulating the intrinsic spin state of Pt through the interaction with the local high spin 4f orbital electrons in rare-earth metals, with the aim of boosting the spin-related oxygen reduction reaction, thus fundamentally contributing to the understanding of new descriptors that control ORR activity.

ATF4 renders human T-cell acute lymphoblastic leukemia cell resistance to FGFR1 inhibitors through amino acid metabolic reprogramming.

Abnormalities of FGFR1 have been reported in multiple malignancies, suggesting FGFR1 as a potential target for precision treatment, but drug resistance remains a formidable obstacle. In this study, we explored whether FGFR1 acted a therapeutic target in human T-cell acute lymphoblastic leukemia (T-ALL) and the molecular mechanisms underlying T-ALL cell resistance to FGFR1 inhibitors. We showed that FGFR1 was significantly upregulated in human T-ALL and inversely correlated with the prognosis of patients. Knockdown of FGFR1 suppressed T-ALL growth and progression both in vitro and in vivo. However, the T-ALL cells were resistant to FGFR1 inhibitors AZD4547 and PD-166866 even though FGFR1 signaling was specifically inhibited in the early stage. Mechanistically, we found that FGFR1 inhibitors markedly increased the expression of ATF4, which was a major initiator for T-ALL resistance to FGFR1 inhibitors. We further revealed that FGFR1 inhibitors induced expression of ATF4 through enhancing chromatin accessibility combined with translational activation via the GCN2-eIF2α pathway. Subsequently, ATF4 remodeled the amino acid metabolism by stimulating the expression of multiple metabolic genes ASNS, ASS1, PHGDH and SLC1A5, maintaining the activation of mTORC1, which contributed to the drug resistance in T-ALL cells. Targeting FGFR1 and mTOR exhibited synergistically anti-leukemic efficacy. These results reveal that FGFR1 is a potential therapeutic target in human T-ALL, and ATF4-mediated amino acid metabolic reprogramming contributes to the FGFR1 inhibitor resistance. Synergistically inhibiting FGFR1 and mTOR can overcome this obstacle in T-ALL therapy.

Genome-wide analysis of cuticle protein family genes in rice stem borer Chilo suppressalis: Insights into their role in environmental adaptation and insecticidal stress response.

Insect cuticle plays a key role in insect survival, adaptation and prosperity by serving as the exoskeleton and the first barrier against environmental stresses. As the major components of insect cuticle, the diverse structural cuticle proteins (CPs) contribute to variation in physical properties and functions of cuticle. However, the roles of CPs in cuticular versatility, especially in the stress response or adaption, remain incompletely understood. In this study, we performed a genome-wide analysis of CP superfamily in the rice-boring pest Chilosuppressalis. A total of 211 CP genes were identified and their encoding proteins were classified into eleven families and three subfamilies (RR1, RR2, and RR3). The comparative genomic analysis of CPs revealed that C. suppressalis had fewer CP genes compared to other lepidopteran species, which largely resulted from a less expansion of his-rich RR2 genes involved in cuticular sclerotization, suggesting long-term boring life of C. suppressalis inside rice hosts might evolutionarily prefer cuticular elasticity rather than cuticular sclerotization. We also investigated the response pattern of all CP genes under insecticidal stresses. >50 % CsCPs were upregulated at least 2-fold under insecticidal stresses. Notably, the majority of the highly upregulated CsCPs formed gene pairs or gene clusters on chromosomes, indicating the rapid response of adjacent CsCPs to insecticidal stress. Most high-response CsCPs encoded AAPA/V/L motifs that are related to cuticular elasticity and >50 % of the sclerotization-related his-rich RR2 genes were also upregulated. These results suggested the potential roles of CsCPs in balancing the elasticity and sclerotization of cuticles, which is essential for the survival and adaptation of plant borers including C. suppressalis. Our study provides valuable information for further developing cuticle-based strategies of both pest management and biomimetic applications.

The effect of ambient PM2.5 exposure on survival of lung cancer patients after lobectomy.

Exposure to fine particulate matter (PM2.5) is linked to lung cancer incidence and mortality. However, the impact of PM2.5 exposure on lung cancer patients after lobectomy, which remains the primary treatment for early-stage lung cancer, is unknown. Therefore, we investigated the correlation between PM2.5 exposure and the survival of lung cancer patients after lobectomy. This study included 3,327 patients with lung cancer who underwent lobectomy procedures. We converted residential addresses into coordinates and estimated individual patients' daily PM2.5 and O3 exposure levels. A Cox multivariate regression model was used to analyze the specific monthly association between PM2.5 exposure and lung cancer survival. Every 10 µg/m3 increase in monthly PM2.5 concentration in the first and second months after lobectomy increased the risk of death (hazard ratio [HR]: 1.043, 95% confidence interval [CI]: 1.019-1.067 and HR: 1.036, 95% CI: 1.013-1.060, respectively). Non-smokers, younger patients, and patients with longer hospitalization durations had worse survival rates when exposed to greater concentrations of PM2.5. High postoperative PM2.5 exposure immediately after lobectomy reduced the survival of patients with lung cancer. Patients living in areas with high PM2.5 should be offered the opportunity to transfer to areas with better air quality after undergoing lobectomies, to prolong their survival times.

Passive source localization based on multipath arrival angles with a vertical line array using sparse Bayesian learning.

In deep water, multipath time delays or frequency-domain interference periods of the acoustic intensity combined with multipath arrival angles are typically used for source localization. However, depth estimate is hard to achieve for a narrowband source at a remote part of the direct arrival zone as the required bandwidth increases with the source range. In this paper, a passive source localization method with a vertical line array, suitable for both broadband and narrowband sources, is proposed. Based on the variation trends of multipath angles with source range and depth, source localization is achieved by only matching the measured angles of the direct path and surface-reflected path with model-based values of a predefined grid of potential source locations. Considering the angle resolution limited by the array aperture and the presence of coherent multipath, sparse Bayesian learning is used and compared with the conventional beamforming and the minimum-variance distortionless-response beamforming to resolve and estimate the multipath angles. Simulations and experimental data of explosive sources collected by a vertical line array in the South China Sea are carried out to illustrate the method and demonstrate the performance.

Corrigendum: Delayed diagnosis and treatment of cancer patients during the COVID-19 pandemic in Henan, China: An interrupted time series analysis.

[This corrects the article DOI: 10.3389/fpubh.2022.881718.].

Customized reaction route for ruthenium oxide towards stabilized water oxidation in high-performance PEM electrolyzers.

The poor stability of Ru-based acidic oxygen evolution (OER) electrocatalysts has greatly hampered their application in polymer electrolyte membrane electrolyzers (PEMWEs). Traditional understanding of performance degradation centered on influence of bias fails in describing the stability trend, calling for deep dive into the essential origin of inactivation. Here we uncover the decisive role of reaction route (including catalytic mechanism and intermediates binding strength) on operational stability of Ru-based catalysts. Using MRuOx (M = Ce4+, Sn4+, Ru4+, Cr4+) solid solution as structure model, we find the reaction route, thereby stability, can be customized by controlling the Ru charge. The screened SnRuOx thus exhibits orders of magnitude lifespan extension. A scalable PEMWE single cell using SnRuOx anode conveys an ever-smallest degradation rate of 53 µV h-1 during a 1300 h operation at 1 A cm-2.

Regulating the MXene-Zinc Interfacial Structure toward a Highly Revisable Metal Anode of Zinc-Air Batteries.

Rechargeable aqueous Zn-air batteries have been regarded as one of the most promising systems for flexible energy storage devices due to their high specific energy, safety, and cost effectiveness. However, Zn metal anodes exposed to strong alkaline electrolytes suffer from several issues such as corrosion, dissolution, and passivation, resulting in extremely poor cycle reversibility. Motivated by this challenge, we herein strategically design an MXene/Zn metal anode interfacial structure with single/few-layer Ti3C2Tx MXene as a protective layer. Such a design not only isolates the direct contact between Zn metal anodes and electrolytes but also inhibits zincate dissolution due to the ion screening function of Ti3C2Tx, potentially addressing the stubborn issues that Zn anodes faced with. As a result, the Ti3C2Tx-protected Zn metal anode exhibits superior cycle stability (stable for more than 400 cycles) to the bare Zn counterpart (20 cycles) at a high current density of 5.0 mA cm-2. When integrated into Zn-air coin cells, it has a high depth of discharge of 91% and operates stably for 140 cycles with small resistance. More interestingly, the excellent flexibility of the as-designed Ti3C2Tx-protected Zn metal anode endows the quasi-solid-state batteries with admirable voltage stability at different bending angles from 0 to 180°.

Colonization of Fusobacterium nucleatum is an independent predictor of poor prognosis in gastric cancer patients with venous thromboembolism: a retrospective cohort study.

BACKGROUND: Fusobacterium nucleatum (F. nucleatum) often colonizes cancerous gastric tissues and is characterized by the promotion of platelet aggregation and the development of visceral thrombosis. Venous thromboembolism (VTE) leads to a significant increase in the mortality of gastric cancer (GC) patients. However, the relationship between the colonization of F. nucleatum and the prognosis of GC patients is still unknown. AIM: The aim of this study was to explore whether the colonization of F. nucleatum is related to the prognosis of GC patients complicated with VTE and to explore other potential risk factors. METHODS: From 2017-2021, the data of 304 patients with new VTEs during the treatment of GC at the Affiliated Cancer Hospital of Zhengzhou University were collected. Fluorescence in situ hybridization of F. nucleatum was performed on pathological sections of cancer tissues from the patients. Survival analysis methods, including the Kaplan‒Meier method and Cox proportional hazard model, were performed. RESULTS: F. nucleatum colonization was significantly associated with splanchnic vein thrombosis, higher platelet-lymphocyte ratio (PLR), and lower absolute lymphocyte count. In the multivariable Cox model, F. nucleatum colonization was found to be an independent risk factor for the prognosis of GC, with an adjusted HR of 1.77 (95% CI, 1.17 to 2.69 [P = 0.007]). In addition, patients with high PLR (HR: 2.65, P = 0.004) or VTE occurring during four cycles of chemotherapy (HR: 2.32, P = 0.012) exhibited shorter survival. Conversely, those experiencing VTE later (HR per month from diagnosis of GC: 0.95, P = 0.006) or using IVC filters (HR: 0.27, P = 0.011) had longer survival. CONCLUSION: Colonization of F. nucleatum in GC tissues was associated with lower absolute lymphocyte count and higher PLR in GC patients with VTE. F. nucleatum colonization also appeared to be associated with the development of VTE in specific sites, in particular the splanchnic vein. Colonization of F. nucleatum may potentially represent an independent predictor of poor prognosis in GC patients. Additional research is necessary to validate these findings.

Challenges and Strategies of Anion Exchange Membranes in Hydrogen-electricity Energy Conversion Devices.

Alkaline hydrogen-electricity energy conversion technologies, involving anion exchange membrane fuel cells (AEMFCs) and anion exchange membrane water electrolyzers (AEMWEs) are more appealing than the acidic counterparts due to the elimination of precious metal catalysts. However, the physicochemical properties of anion exchange membrane (AEMs), i.e., ionic conductivity, mechanical strength, stability, etc., are inferior to that of proton exchange membranes (PEMs), thus hindering these alkaline technologies from practical employment. To promote their development, we summarize the main challenges and the corresponding strategies of AEMs for the application of AEMFCs and AEMWEs in this review. The hydroxide transportation mechanism, ion exchange capacity, hydration and microscopic morphology that are relevant to the ionic conductivity are discussed firstly. Following the ionic conductivity, another obstacle, stability of AEMs is comprehensively described in terms of alkaline stability, mechanical stability and electrochemical stability. Upon integrating into the devices, water management, carbonation effect and membrane-electrode interface that are critical to the cell performance are highlighted as well. This review is anticipated to provide insights into the AEM design for hydrogen-electric energy conversion devices, thus accelerating the widespread commercialization of these promising technologies.

Co-based Catalysts for Selective H2 O2 Electroproduction via 2-electron Oxygen Reduction Reaction.

Electrochemical production of hydrogen peroxide (H2 O2 ) via two-electron oxygen reduction reaction (ORR) process is emerging as a promising alternative method to the conventional anthraquinone process. To realize high-efficiency H2 O2 electrosynthesis, robust and low cost electrocatalysts have been intensively pursued, among which Co-based catalysts attract particular research interests due to the earth-abundance and high selectivity. Here, we provide a comprehensive review on the advancement of Co-based electrocatalyst for H2 O2 electroproduction. The fundamental chemistry of 2-electron ORR is discussed firstly for guiding the rational design of electrocatalysts. Subsequently, the development of Co-based electrocatalysts involving nanoparticles, compounds and single atom catalysts is summarized with the focus on active site identification, structure regulation and mechanism understanding. Moreover, the current challenges and future directions of the Co-based electrocatalysts are briefly summarized in this review.

Enhanced Acidic Water Oxidation by Dynamic Migration of Oxygen Species at the Ir/Nb2 O5-x Catalyst/Support Interfaces.

Catalyst/support interaction plays a vital role in catalysis towards acidic oxygen evolution (OER), and the performance reinforcement is currently interpreted by either strain or electron donation effect. We herein report that these views are insufficient, where the dynamic evolution of the interface under potential bias must be considered. Taking Nb2 O5-x supported iridium (Ir/Nb2 O5-x ) as a model catalyst, we uncovered the dynamic migration of oxygen species between IrOx and Nb2 O5-x during OER. Direct spectroscopic evidence combined with theoretical computation suggests these migrations not only regulate the in situ Ir structure towards boosted activity, but also suppress its over-oxidation via spontaneously delivering excessive oxygen from IrOx to Nb2 O5-x . The optimized Ir/Nb2 O5-x thus demonstrated exceptional performance in scalable water electrolyzers, i.e., only need 1.839 V to attain 3 A cm-2 (surpassing the DOE 2025 target), and no activity decay during a 2000 h test at 2 A cm-2 .