Lutetium-Induced Ultrafine PtRu Nanoclusters with a High Electrochemical Surface Area for Direct Methanol Fuel Cells at Alleviated Temperatures.

PtRu alloys have been recognized as the state-of-the-art catalysts for the methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). However, their applications in DMFCs are still less efficient in terms of both catalytic activity and durability. Rare earth (RE) metals have been recognized as attractive elements to tune the catalytic activity, while it is still a world-class challenge to synthesize well-dispersed Pt-RE alloys. Herein, we developed a novel hydrogen-assisted magnesiothermic reduction strategy to prepare a highly dispersed carbon-supported lutetium-doped PtRu catalyst with ultrafine nanoclusters and atomically dispersed Ru sites. The PtRuLu catalyst shows an outstanding high electrochemical surface area (ECSA) of 239.0 m2 gPt-1 and delivers an optimized MOR mass activity and specific activity of 632.5 mA mgPt-1 and 26 A cmPt-2 at 0.4 V vs saturated calomel electrode (SCE), which are 3.6 and 3.5 times of commercial PtRu-JM and an order higher than PtLu, respectively. These novel catalysts have been demonstrated in a high-temperature direct methanol fuel cell running in a temperature range of 180-240 °C, achieving a maximum power density of 314.3 mW cm-2. The AC-STEM imaging, in situ ATR-IR spectroscopy, and DFT calculations disclose that the high performance is resulted from the highly dispersed PtRuLu nanoclusters and the synergistic effect of the atomically dispersed Ru sites with PtRuLu nanoclusters, which significantly reduces the CO* intermediates coverage due to the promoted water activation to form the OH* to facilitate the CO* removal.

[Optimization of the fermentative production of L-methionine by engineered Escherichia coli].

As the only essential amino acid containing elemental sulphur, L-methionine has important physiological and biochemical functions in living organisms. However, the fermentative production of L-methionine has not met the requirements of industrial production because of its low production level. In this paper, the fermentation process of an efficient L-methionine producing strain E. coli W3110ΔIJAHFEBC trc-fliY trc-malY/PAM glyA-22 metF constructed previously was systematically optimized. Based on the optimal initial glucose concentration, the effects of different fed-batch fermentation processes, including DO-Stat, pH-Stat, controlling residual sugar control at different level and feeding glucose with constant rate, on L-methionine fermentation were studied. It was found that the control of glucose concentration greatly affected the fermentation process. Subsequently, an optimal fed-batch fermentation process was developed, where the L-methionine titer was increased to 31.71 g/L, the highest yield reported to date, while the fermentation time was shortened to 68 h. Meanwhile, a fermentation kinetics model under the optimal fed-batch fermentation conditions was established, which fitted well with the biosynthesis process of L-methionine. This study may facilitate further development of the fermentative production of L-methionine.

Uncovering Photoelectronic and Photothermal Effects in Plasmon-Mediated Electrocatalytic CO2 Reduction.

Plasmon-mediated electrocatalysis that rests on the ability of coupling localized surface plasmon resonance (LSPR) and electrochemical activation, emerges as an intriguing and booming area. However, its development seriously suffers from the entanglement between the photoelectronic and photothermal effects induced by the decay of plasmons, especially under the influence of applied potential. Herein, using LSPR-mediated CO2 reduction on Ag electrocatalyst as a model system, we quantitatively uncover the dominant photoelectronic effect on CO2 reduction reaction over a wide potential window, in contrast to the leading photothermal effect on H2 evolution reaction at relatively negative potentials. The excitation of LSPR selectively enhances the CO faradaic efficiency (17-fold at -0.6 VRHE ) and partial current density (100-fold at -0.6 VRHE ), suppressing the undesired H2 faradaic efficiency. Furthermore, in situ attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals a plasmon-promoted formation of the bridge-bonded CO on Ag surface via a carbonyl-containing C1 intermediate. The present work demonstrates a deep mechanistic understanding of selective regulation of interfacial reactions by coupling plasmons and electrochemistry.

Improving the Efficiencies of Water Splitting and CO2 Electrolysis by Anodic O2 Bubble Management.

This study systematically explores the impact of the anodic flow field design on the transport of O2 bubble and subsequent energy efficiency in electrolysis devices. Two distinct configurations, namely a conventional serpentine flow panel and an interdigitated flow panel, are integrated at the anode side of the electrolyzer. The interdigitated flow field exhibits superior performance in both alkaline water splitting and CO2 reduction despite the experience of an increased pressure drop. Numerical simulations reveal that the enhanced convective flow of the O2 bubbles induced by a forced anolyte flow through the porous electrode within the interdigitated panel design resulted in a 3 orders of magnitude increase in the level of the O2 bubble transport compared to the serpentine configuration. These findings not only underscore the significance of flow field design on bubble management but also provide a basis for advancing the electrolysis efficiency at industrial-level current densities.

Metabolic changes of glycerophospholipids during the reparative phase after myocardial infarction injury.

Introduction: Myocardial infarction (MI) is a fatal manifestation of coronary heart disease, and its underlying mechanism is still largely unknown. Lipid levels and composition alterations predict the risk of MI complications. Glycerophospholipids (GPLs) are important bioactive lipids and play a crucial role in the development of cardiovascular diseases. However, the metabolic changes in the GPLs profile during post-MI injury remain unknown. Methods: In the current study, we constructed a classic MI model by ligating the left anterior descending branch and assessed the alterations in both plasma and myocardial GPLs profiles during the reparative phase post-MI by liquid chromatography-tandem mass spectrometry analysis. Results: We found that myocardial GPLs, but not plasma GPLs, were markedly changed after MI injury. Importantly, MI injury is associated with decreased phosphatidylserine (PS) levels. Consistently, the expression of phosphatidylserine synthase 1 (PSS1), which catalyzes the formation of PS from its substrate phosphatidylcholine, was significantly reduced in heart tissues after MI injury. Furthermore, oxygen-glucose deprivation (OGD) inhibited PSS1 expression and reduced PS levels in primary neonatal rat cardiomyocytes, while overexpression of PSS1 restored the inhibition of PSS1 and the reduction in PS levels caused by OGD. Moreover, overexpression of PSS1 abrogated, whereas knockdown of PSS1 aggravated, OGD-induced cardiomyocyte apoptosis. Conclusions: Our findings revealed that GPLs metabolism was involved in the reparative phase post-MI, and cardiac decreased PS levels, resulting from inhibition of PSS1, are important contributor to the reparative phase post-MI. PSS1 overexpression represents a promising therapeutic strategy to attenuate MI injury.

Hyphenated DEMS and ATR-SEIRAS techniques for in situ multidimensional analysis of lithium-ion batteries and beyond.

A wide spectrum of state-of-the-art characterization techniques have been devised to monitor the electrode-electrolyte interface that dictates the performance of electrochemical devices. However, coupling multiple characterization techniques to realize in situ multidimensional analysis of electrochemical interfaces remains a challenge. Herein, we presented a hyphenated differential electrochemical mass spectrometry and attenuated total reflection surface enhanced infrared absorption spectroscopy analytical method via a specially designed electrochemical cell that enables a simultaneous detection of deposited and volatile interface species under electrochemical reaction conditions, especially suitable for non-aqueous, electrolyte-based energy devices. As a proof of concept, we demonstrated the capability of the homemade setup and obtained the valuable reaction mechanisms, by taking the tantalizing reactions in non-aqueous lithium-ion batteries (i.e., oxidation and reduction processes of carbonate-based electrolytes on Li1+xNi0.8Mn0.1Co0.1O2 and graphite surfaces) and lithium-oxygen batteries (i.e., reversibility of the oxygen reaction) as model reactions. Overall, we believe that the coupled and complementary techniques reported here will provide important insights into the interfacial electrochemistry of energy storage materials (i.e., in situ, multi-dimensional information in one single experiment) and generate much interest in the electrochemistry community and beyond.

Alox15/15-HpETE Aggravates Myocardial Ischemia-Reperfusion Injury by Promoting Cardiomyocyte Ferroptosis.

BACKGROUND: Myocardial ischemia-reperfusion (I/R) injury causes cardiac dysfunction to myocardial cell loss and fibrosis. Prevention of cell death is important to protect cardiac function after I/R injury. The process of reperfusion can lead to multiple types of cardiomyocyte death, including necrosis, apoptosis, autophagy, and ferroptosis. However, the time point at which the various modes of cell death occur after reperfusion injury and the mechanisms underlying ferroptosis regulation in cardiomyocytes are still unclear. METHODS: Using a left anterior descending coronary artery ligation mouse model, we sought to investigate the time point at which the various modes of cell death occur after reperfusion injury. To discover the key molecules involved in cardiomyocyte ferroptosis, we performed a metabolomics study. Loss/gain-of-function approaches were used to understand the role of 15-lipoxygenase (Alox15) and peroxisome proliferator-activated receptor gamma coactivator 1-alpha (Pgc1α) in myocardial I/R injury. RESULTS: We found that apoptosis and necrosis occurred in the early phase of I/R injury, and that ferroptosis was the predominant form of cell death during the prolonged reperfusion. Metabolomic profiling of eicosanoids revealed that Alox15 metabolites accumulated in ferroptotic cardiomyocytes. We demonstrated that Alox15 expression was specifically increased in the injured area of the left ventricle below the suture and colocalized with cardiomyocytes. Furthermore, myocardial-specific knockout of Alox15 in mice alleviated I/R injury and restored cardiac function. 15-Hydroperoxyeicosatetraenoic acid (15-HpETE), an intermediate metabolite derived from arachidonic acid by Alox15, was identified as a trigger for cardiomyocyte ferroptosis. We explored the mechanism underlying its effects and found that 15-HpETE promoted the binding of Pgc1α to the ubiquitin ligase ring finger protein 34, leading to its ubiquitin-dependent degradation. Consequently, attenuated mitochondrial biogenesis and abnormal mitochondrial morphology were observed. ML351, a specific inhibitor of Alox15, increased the protein level of Pgc1α, inhibited cardiomyocyte ferroptosis, protected the injured myocardium, and caused cardiac function recovery. CONCLUSIONS: Together, our results established that Alox15/15-HpETE-mediated cardiomyocyte ferroptosis plays an important role in prolonged I/R injury.

The Combined Effect of Nanobubble-IR783-HPPH-Affibody Complex and Laser on HER2-Positive Breast Cancer.

Introduction: Nanobubble is an innovative ultrasound contrast agent that triggers the development of targeted imaging of HER2-positive breast cancer by combining with HER2 affibody and IR783. HPPH is a second-generation photosensitiser that is effective in treating tumours. Hence, the nanobubble-IR783-HPPH-affibody (NIHA) complex demonstrates considerable potential in the treatment of HER2-positive breast cancer. Methods: We fabricated the NIHA complex via an advanced thin-film hydration method and detected its characteristics such as particle size, morphology, stability, and cytotoxicity. Moreover, the effect of NIHA complex with laser on HER2-positive breast cancer was confirmed via in vitro and in vivo experiments. Results: The NIHA complex was spheroid, stable and exhibited no cytotoxicity; moreover, its particle size was 524.8 ± 53.3 nm (n = 5). In combination with laser treatment, NIHA complex reduced the cell viability and tumour volume, induced apoptosis of HER2-positive breast cancer cells, and prolonged survival of nude mice. Conclusion: The newly prepared NIHA complex with laser treatment has the potential on treating HER2-positive breast cancer.

Plasmon-Enhanced C-C Bond Cleavage toward Efficient Ethanol Electrooxidation.

Ethanol, as a sustainable biomass fuel, is endowed with the merits of theoretically high energy density and environmental friendliness yet suffers from sluggish kinetics and low selectivity toward the desired complete electrooxidation (C1 pathway). Here, the localized surface plasmon resonance (LSPR) effect is explored as a manipulating knob to boost electrocatalytic ethanol oxidation reaction in alkaline media under ambient conditions by appropriate visible light. Under illumination, Au@Pt nanoparticles with plasmonic core and active shell exhibit concurrently higher activity (from 2.30 to 4.05 A mgPt-1 at 0.8 V vs RHE) and C1 selectivity (from 9 to 38% at 0.8 V). In situ attenuated total reflection-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) provides a molecular level insight into the LSPR promoted C-C bond cleavage and the subsequent CO oxidation. This work not only extends the methodology hyphenating plasmonic electrocatalysis and in situ surface IR spectroscopy but also presents a promising approach for tuning complex reaction pathways.

Coadministration of Compound Danshen dripping pills and bezafibrate has a protective effect against diabetic retinopathy.

Diabetic retinopathy (DR) is increasingly becoming a main complication of diabetes, and is difficult to cure. In our research, network pharmacology analysis suggested that both compound Danshen dripping pills (CDDP) and bezafibrate (BZF) have potential protective effects against DR and the two drugs may act synergistically. The pharmacological effects of the coadministration of CDDP and BZF were elucidated in db/db mice, which simulate DR. Fluorescein fundus angiography showed that coadministration attenuated vascular leakage. Optical coherence tomography and hematoxylin and eosin staining showed that coadministration improved retinal thickness better than CDDP monotherapy. In addition, cell fluorescence images of reactive oxygen species revealed that coadministration of CDDP and BZF had more potent effects against oxidative stress than CDDP monotherapy. Metabolomics analysis showed that coadministration reduced the ratio of oxidized glutathione to reduced glutathione further than CDDP monotherapy. Coadministration of CDDP and BZF may provide additional protective effects by resisting vascular leakage, increasing retinal thickness, and inhibiting inflammation and oxidative stress in DR.

In Situ Wide-Frequency Surface-Enhanced Infrared Absorption Spectroscopy Enables One to Decipher the Interfacial Structure of a Cu Plating Additive.

In situ spectroscopic characterization of the interfacial structure of an organic additive at a Cu electrode is essential for a mechanistic understanding of Cu superfilling at the molecular level. In this work, we demonstrate wide-frequency attenuated total reflection surface-enhanced infrared absorption spectroscopy (wf-ATR-SEIRAS) to elucidate the dissociative adsorption of bis(sodium sulfopropyl)-disulfide (a typical accelerator) on a Cu electrode in conjunction with the electrochemical quartz crystal microbalance measurement and modeling calculations. The wf-ATR-SEIRAS clearly identifies the peaks featuring the sulfonate and methylene groups as well as the C-Ssulfonate and C-Sthiol vibrations of the adsorbate. Analysis of relative peak intensities from 1100 to 650 cm-1 reveals a more tilted alkyl chain axis for the thiolate on Cu than that on Au, which is supported by comparative density functional theory calculations. This work opens a new avenue for the wf-ATR-SEIRAS to study interfacial structures of electroplating additives related to advanced microelectronics manufacture.

Colon specific delivery of miR-155 inhibitor alleviates estrogen deficiency related phenotype via microbiota remodeling.

Compelling data have indicated menopause-associated increase in cardiovascular disease in women, while the underlying mechanisms remain largely unknown. It is established that changes of intestinal microbiota affect cardiovascular function in the context of metabolic syndrome. We here aimed to explore the possible link between host intestinal function, microbiota, and cardiac function in the ovariectomy (OVX) mouse model. Mice were ovariectomized to induce estrogen-related metabolic syndrome and cardiovascular defect. Microbiota was analyzed by 16s rRNA sequencing. miRNA and mRNA candidates expression were tested by qPCR. Cardiac function was examined by echocardiography. Colon specific delivery of miRNA candidates was achieved by oral gavage of Eudragit S100 functionalized microspheres. In comparison with the sham-operated group, OVX mice showed compromised cardiac function, together with activated inflammation in the visceral adipose tissue and heart. Lactobacillus abundance was significantly decreased in the gut of OVX mice. Meanwhile, miR-155 was mostly upregulated in the intestinal epithelium and thus the feces over other candidates, which in turn decreased Lactobacillus abundance in the intestine when endocytosed. Oral delivery of miR-155 antagonist restored the protective microbiota and thus protected the cardiac function in the OVX mice. This study has established a possible regulatory axis of intestinal miRNAs-microbiota-estrogen deficiency related phenotype in the OVX model. Colon specific delivery of therapeutic miRNAs would possibly restore the microbiota toward protective phenotype in the context of metabolic syndrome.

Electrolyte-Layer-Tunable ATR-SEIRAS for Simultaneous Detection of Adsorbed and Dissolved Species in Electrochemistry.

A balanced detection of both adsorbates and dissolved species is very important for the clarification of the electrochemical reaction mechanism yet remains a major challenge for different modes of electrochemical infrared (IR) spectroscopy. Among others, conventional attenuated total reflection-surface-enhanced IR absorption spectroscopy (ATR-SEIRAS) is far less sensitive to low-concentration solution species than to surface species. We report herein an electrochemical wide-frequency ATR-SEIRAS with a novel thin-layer flow cell design, fulfilling the simultaneous detection of the variations of surface and solution species. This setup consists of a silicon wafer (with one side micromachined and the other side metallized), a thin-layer electrolyte structure with tunable thickness and flow rate, and a tilt-correction system based on laser collimation, enabling a well-controlled mass transport within the electrolyte layer and the spectral differentiation of solution species from adsorbates. Using acidic methanol oxidation on a Pt film electrode as a model system, besides SEIRA bands for adsorbed CO and formate intermediates, IR spectral signals for dissolved products CO2, formic acid, and methyl formate can be readily identified for a quiescent electrolyte layer of ∼20 µm, which are otherwise undetected with conventional ATR-SEIRAS, as indicated by the trend of spectral features with increasing thickness or flow rate.

Preliminary study of carotid variables under ultrasound analysis as predictors for the risk of coronary arterial atherosclerosis.

BACKGROUND: Carotid atherosclerosis by ultrasound scanning can be considered as an ideal window to reflect systemic artery atherosclerosis, which has aroused wide concern for predicting the severity of coronary artery atherosclerosis clinically. Ultrasound radio frequency (RF) data technology has enabled us to evaluate the carotid structure and elastic function precisely, for predicting the severity of coronary artery atherosclerosis. METHODS: Patients with suspected coronary artery disease (CAD) underwent coronary angiography and were assigned to four groups according to whether atherosclerotic plaque was found or not and it caused stenosis. Carotid artery intima-media thickness (IMT) and arterial stiffness were investigated by quality intima-media thickness (QIMT) and quality arterial stiffness (QAS) techniques during ultrasound scanning. Univariable and multivariable modeling were used to investigate correlations of carotid parameters to coronary artery atherosclerosis. Receive operating characteristic (ROC) curves were used to evaluate diagnostic performance of these ultrasound variables. RESULTS: Carotid IMT and stiffness variables pulse wave velocity (PWV), α, ß and compliance coefficient (CC) were statistically different between every two-group's comparisons. IMT correlated with stiffness variables significantly with r = 0.70, 0.77, 0.63, and -0.39, respectively. All variables correlated with the severity of coronary atherosclerosis with the odd ratio (OR) of 1.73, 1.67, 1.19, 1.23, and 0.56 accordingly as IMT, PWV, α, ß and CC were concerned. The AUC of IMT, PWV, α, ß and CC were 0.9257, 0.8910, 0.8016, 0.9383, 0.8581 with correctly classified rate of 88.16%, 83.77%, 78.07%, 86.84%, and 81.58%, respectively. CONCLUSIONS: Carotid artery IMT and stiffness variable PWV, α, ß and CC presented favorable predicting and differentiating values for patients with coronary atherosclerosis of different severity.

Rhombohedral Pd-Sb Nanoplates with Pd-Terminated Surface: An Efficient Bifunctional Fuel-Cell Catalyst.

Developing high-performance electrocatalysts for the ethanol oxidation reaction (EOR) and the oxygen reduction reaction (ORR) is essential for the commercialization of direct ethanol fuel cells, but it is still formidably challenging. In this work, a novel Pd-Sb hexagonal nanoplate for boosting both cathodic and anodic fuel cell reactions is prepared. Detailed characterizations reveal that the nanoplates have ordered rhombohedral phase of Pd8 Sb3 (denoted as Pd8 Sb3 HPs). The Pd8 Sb3 HPs exhibit much enhanced activity toward the oxidation of various alcohols. Particularly, Pd8 Sb3 HPs/C displays superior specific and mass activities of 29.3 mA cm-2 and 4.5 A mgPd -1 toward the EOR, which are 7.0 and 11.3 times higher than those of commercial Pd/C, and 9.8 and 3.8 times higher than those of commercial Pt/C, respectively, representing one of the best EOR catalysts reported to date. In situ electrochemical attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements reveal that Pd8 Sb3 HPs/C can effectively promote the C2 pathway of the EOR. As revealed by density functional theory calculations, the high EOR activity of the Pd8 Sb3 HPs can be ascribed to the reduced energy barrier of ethanol dehydrogenation. Additionally, Pd8 Sb3 HPs/C also shows superior performance in the ORR. This work advances the controllable synthesis of the Pd-Sb nanostructure, giving huge impetus for the design of high-efficiency electrocatalysts for energy conversion and beyond.

The severity of portal hypertension by a non-invasive assessment: acoustic structure quantification analysis of liver parenchyma.

BACKGROUND: Acoustic structure quantification (ASQ) has been applied to evaluate liver histologic changes by analyzing the speckle pattern seen on B-mode ultrasound. We aimed to assess the severity of portal hypertension (PHT) through hepatic ultrasonography. METHODS: Sixty patients diagnosed with PHT and underwent surgical treatment with portosystemic shunts were enrolled. Portal pressure (PP) was measured intraoperatively. Patients were divided into subgroups according to the severity of gastroesophageal varices and Child-Pugh class. Three difference ratio (Cm2) values on ASQ histogram mode were analyzed for their relationships with PP, degree of gastroesophageal varices and Child-Pugh liver function. Thirty healthy volunteers matched with the patients for gender and age were enrolled as controls. Comparisons among groups and correlation of the parameters with PP were analyzed. Area under the receive operating characteristic curve was used to evaluate the predicting value of ASQ parameters. RESULTS: In the patients, the ASQ parameters peak Cm2 (Cm2max), mean Cm2 (Cm2mean) and the highest occurred Cm2 value of the obtained red curve (RmaxCm2) were all greatly increased (P < 0.0001, P < 0.0001, P = 0.027). Multiple comparisons indicated that, regardless of Child-Pugh class and degree of gastroesophageal varices, the patients had significantly increased Cm2max and Cm2mean compared with the controls (all P < 0.0001). No differences among subgroups were observed. Cm2max was significantly statistically correlated with PP (r = 0.3505, P < 0.01), degree of varices (r = 0.4998, P < 0.0001). Youden's index for Cm2max with a cut-off value of 140.3 for predicting the presence of PHT, gastroesophageal varices and liver function equal to or worse than Child-Pugh class B were 0.8, 0.91 and 0.84, respectively. CONCLUSIONS: ASQ analysis of ultrasonographic images may have a role in the evaluation of the severity of PHT by detecting liver histologic changes in the speckle pattern caused by cirrhosis.

Study on the P-S-N Curve of Sucker Rod Based on Three-Parameter Weibull Distribution.

During the oil production process, sucker rods are subjected to cyclic alternating load. After a certain number of cycles, a sucker rod can experience fatigue failure. The number of cycles is called fatigue life (N), and the accurate relationship between maximum stress (S) and fatigue life (N) under a certain reliability (P), namely the P-S-N curve, is an important basis for the reliability analysis and fatigue life prediction of sucker rods. The Basquin model, based on log-normal distribution, is widely used for fitting the P-S-N curves of sucker rods. Due to the limitation of this model, it is difficult to extrapolate the conclusion obtained from a finite fatigue region to the high-cycle or ultra-high-cycle fatigue region, which makes it impossible to estimate the fatigue limit of the sucker rod. Compared to the log-normal distribution, Weibull distribution causes the sucker rod to have a minimum safety life, namely the safety life at 100% survival rate, which complies with the fatigue characteristics of the sucker rod and is more in line with the actual situation. In this study, the fatigue data for ultra-high-strength HL and HY grade sucker rods were obtained through experimental fatigue tests. A new fatigue life model was established and the P-S-N curves of two types of ultra-high strength sucker rods were obtained. For HL- and HY-type ultra-high strength sucker rods, the average error between the fitting result and fatigue test value is 1.25% and 4.39%, respectively. Compared to the S-N curve fitting result obtained from the Basquin model commonly used for sucker rods, the new model based on three-parameter Weibull distribution provides better fitting precision and can estimate fatigue limit more accurately, so this model is more suitable for estimating fatigue life and can better guide the design of ultra-high strength sucker rod strings.

Coordination modulation of iridium single-atom catalyst maximizing water oxidation activity.

Single-atom catalysts (SACs) have attracted tremendous research interests in various energy-related fields because of their high activity, selectivity and 100% atom utilization. However, it is still a challenge to enhance the intrinsic and specific activity of SACs. Herein, we present an approach to fabricate a high surface distribution density of iridium (Ir) SAC on nickel-iron sulfide nanosheet arrays substrate (Ir1/NFS), which delivers a high water oxidation activity. The Ir1/NFS catalyst offers a low overpotential of ~170 mV at a current density of 10 mA cm-2 and a high turnover frequency of 9.85 s-1 at an overpotential of 300 mV in 1.0 M KOH solution. At the same time, the Ir1/NFS catalyst exhibits a high stability performance, reaching a lifespan up to 350 hours at a current density of 100 mA cm-2. First-principles calculations reveal that the electronic structures of Ir atoms are significantly regulated by the sulfide substrate, endowing an energetically favorable reaction pathway. This work represents a promising strategy to fabricate high surface distribution density single-atom catalysts with high activity and durability for electrochemical water splitting.

Steering the Glycerol Electro-Reforming Selectivity via Cation-Intermediate Interactions.

Electro-reforming of renewable biomass resources is an alternative technology for sustainable pure H2 production. Herein, we discovered an unconventional cation effect on the concurrent formate and H2 production via glycerol electro-reforming. In stark contrast to the cation effect via forming double layers in cathodic reactions, residual cations at the anode were discovered to interact with the glycerol oxidation intermediates to steer its product selectivity. Through a combination of product analysis, transient kinetics, crown ether trapping experiments, in situ IRRAS and DFT calculations, the aldehyde intermediates were discovered to be stabilized by the Li+ cations to favor the non-oxidative C-C cleavage for formate production. The maximal formate efficiency could reach 81.3 % under ≈60 mA cm-2 in LiOH. This work emphasizes the significance of engineering the microenvironment at the electrode-electrolyte interface for efficient electrolytic processes.

Multi-Omics Approach Reveals Redox Homeostasis Reprogramming in Early-Stage Clear Cell Renal Cell Carcinoma.

Clear cell renal cell carcinoma (ccRCC) is a malignant tumor originating from proximal tubular epithelial cells, and despite extensive research efforts, its redox homeostasis characteristics and protein S-nitrosylation (or S-nitrosation) (SNO) modification remain largely undefined. This serves as a reminder that the aforementioned features demand a comprehensive inspection. We collected tumor samples and paracancerous normal samples from five patients with early-stage ccRCC (T1N0M0) for proteomic, SNO-proteome, and redox-targeted metabolic analyses. The localization and functional properties of SNO proteins in ccRCC tumors and paracancerous normal tissues were elucidated for the first time. Several highly useful ccRCC-associated SNO proteins were further identified. Metabolic reprogramming, redox homeostasis reprogramming, and tumorigenic alterations are the three major characteristics of early-stage ccRCC. Peroxidative damage caused by rapid proliferation coupled with an increased redox buffering capacity and the antioxidant pool is a major mode of redox homeostasis reprogramming. NADPH and NADP+, which were identified from redox species, are both effective biomarkers and promising therapeutic targets. According to our findings, SNO protein signatures and redox homeostasis reprogramming are valuable for understanding the pathogenesis of ccRCC and identifying novel topics that should be seriously considered for the diagnosis and precise therapy of ccRCC.