Constructing micro-nano rod-shaped iron-molybdenum oxide heterojunctions to enhance overall water electrolysis

\ua9 2024 Elsevier Ltd. In this study, we describe the development of ferromolybdenum oxide (FeMoO), which is a heterojunction characterized by a rod-like structure. The synergistic interactions of iron, molybdenum are rod structures enhanced structural defects, mitigated individual component limitations, and improved material performance by optimizing structural configurations and electronic properties. Furthermore, the materials exploited electronic interactions at interfaces composed of different phases. Due to their nano structures with high active surface and optimization of the abundance of active sites, the rod-like FeMoO demonstrated remarkable efficiency for both oxygen and hydrogen evolution, exhibiting low overpotentials of 228 mV and 61 mV, respectively, at a current density of 10 mA cm−2. Moreover, assembling FeMoO as both the anode and cathode FeMoO || FeMoO required a cell voltage of 1.49 V to drive 10 mA cm−2 in an alkaline solution, and this performance persisted for 450 h without significant voltage drop. We established a promising synthetic pathway for the development of dual-transition-metal-based (Fe and Mo) nanorod-like heterostructured electrocatalysts to significantly advance energy conversion technology, holding promise for enhanced water electrolysis applications

Experimental demonstration of flexible bandwidth networking with real-time impairment awareness

We demonstrate a flexible-bandwidth network testbed with a real-time, adaptive control plane that adjusts modulation format and spectrum-positioning to maintain quality of service (QoS) and high spectral efficiency. Here, low-speed supervisory channels and field-programmable gate arrays (FPGAs) enabled real-time impairment detection of high-speed flexible bandwidth channels (flexpaths). Using premeasured correlation data between the supervisory channel quality of transmission (QoT) and flexpath QoT, the control plane adapted flexpath spectral efficiency and spectral location based on link quality. Experimental demonstrations show a back-to-back link with a 360-Gb/s flexpath in which the control plane adapts to varying link optical signal to noise ratio (OSNR) by adjusting the flexpath's spectral efficiency (i.e., changing the flexpath modulation format) between binary phase-shift keying (BPSK), quaternary phase-shift keying (QPSK), and eight phase-shift keying (8PSK). This enables maintaining the data rate while using only the minimum necessary bandwidth and extending the OSNR range over which the bit error rate in the flexpath meets the quality of service (QoS) requirement (e. g. the forward error correction (FEC) limit). Further experimental demonstrations with two flexpaths show a control plane adapting to changes in OSNR on one link by changing the modulation format of the affected flexpath (220 Gb/s), and adjusting the spectral location of the other flexpath (120 Gb/s) to maintain a defragmented spectrum. (C) 2011 Optical Society of Americ

Spectral weight transfer in a disorder-broadened Landau level

In the absence of disorder, the degeneracy of a Landau level (LL) is $N=BA/\phi_0$, where $B$ is the magnetic field, $A$ is the area of the sample and $\phi_0=h/e$ is the magnetic flux quantum. With disorder, localized states appear at the top and bottom of the broadened LL, while states in the center of the LL (the critical region) remain delocalized. This well-known phenomenology is sufficient to explain most aspects of the Integer Quantum Hall Effect (IQHE) [1]. One unnoticed issue is where the new states appear as the magnetic field is increased. Here we demonstrate that they appear predominantly inside the critical region. This leads to a certain ``spectral ordering'' of the localized states that explains the stripes observed in measurements of the local inverse compressibility [2-3], of two-terminal conductance [4], and of Hall and longitudinal resistances [5] without invoking interactions as done in previous work [6-8].Comment: 5 pages 3 figure

An efficient cathode electrocatalyst for anion exchange membrane water electrolyzer

\ua9 2024 The AuthorsA high performance and durable electrocatalyst for the cathodic hydrogen evolution reaction (HER) in anion exchange membrane (AEM) water electrolyzers is crucial for the emerging hydrogen economy. Herein, we synthesized Pt–C core-shell nanoparticles (core: Pt nanoparticles, shell: N-containing carbon) were uniformly coated on hierarchical MoS2/GNF using pyrolysis of h-MoS2/GNF with a Pt-aniline complex. The synthesized Pt–C core-shell@h-MoS2/GNF (with 11.3 % Pt loading) showed HER activity with a lower overpotential of 30 mV at 10 mA cm−2 as compared to the benchmark catalyst 20 % Pt–C (41 mV at 10 mA cm−2) with improved durability over 94 h at 10 mA cm−2. Furthermore, we investigated the structural stability and hydrogen adsorption energy for Pt13 cluster, C90 molecule, h-MoS2 sheet, Pt13–C90 core-shell, and Pt13–C90 core-shell deposited h-MoS2 sheets using density functional theory (DFT) simulations. We investigated the Pt–C core-shell@h-MoS2/GNF catalyst active sites during HER performance using in-situ Raman analysis as well as DFT. We fabricated AEM water electrolyzers with cathode catalysts of Pt–C core-shell@h-MoS2/GNF and evaluated device performance with 0.1 and 1.0 M KOH at 20 and 60 \ub0C. Our work provides a new pathway to design core-shell electrocatalysts for use in AEM water electrolyzers to generate hydrogen

Comparison of type 5d autotransporter phospholipases demonstrates a correlation between high activity and intracellular pathogenic lifestyle

Autotransporters, or type 5 secretion systems, are widespread surface proteins of Gram-negative bacteria often associated with virulence functions. Autotransporters consist of an outer membrane β-barrel domain and an exported passenger. In the poorly studied type 5d subclass, the passenger is a patatin-like lipase. The prototype of this secretion pathway is PlpD of Pseudomonas aeruginosa , an opportunistic human pathogen. The PlpD passenger is a homodimer with phospholipase A1 (PLA1) activity. Based on sequencing data, PlpD-like proteins are present in many bacterial species. We characterized the enzymatic activity, specific lipid binding and oligomeric status of PlpD homologs from Aeromonas hydrophila (a fish pathogen), Burkholderia pseudomallei (a human pathogen) and Ralstonia solanacearum (a plant pathogen) and compared these with PlpD. We demonstrate that recombinant type 5d-secreted patatin domains have lipase activity and form dimers or higher-order oligomers. However, dimerization is not necessary for lipase activity; in fact, by making monomeric variants of PlpD, we show that enzymatic activity slightly increases while protein stability decreases. The lipases from the intracellular pathogens A. hydrophila and B. pseudomallei display PLA2 activity in addition to PLA1 activity. Although the type 5d-secreted lipases from the animal pathogens bound to intracellular lipid targets, phosphatidylserine and phosphatidylinositol phosphates, hydrolysis of these lipids could only be observed for FplA of Fusobacterium nucleatum . Yet, we noted a correlation between high lipase activity in type 5d autotransporters and intracellular lifestyle. We hypothesize that type 5d phospholipases are intracellularly active and function in modulation of host cell signaling events

Voluntary exercise can strengthen the circadian system in aged mice

Consistent daily rhythms are important to healthy aging according to studies linking disrupted circadian rhythms with negative health impacts. We studied the effects of age and exercise on baseline circadian rhythms and on the circadian system's ability to respond to the perturbation induced by an 8 h advance of the light:dark (LD) cycle as a test of the system's robustness. Mice (male, mPer2luc/C57BL/6) were studied at one of two ages: 3.5 months (n = 39) and >18 months (n = 72). We examined activity records of these mice under entrained and shifted conditions as well as mPER2::LUC measures ex vivo to assess circadian function in the suprachiasmatic nuclei (SCN) and important target organs. Age was associated with reduced running wheel use, fragmentation of activity, and slowed resetting in both behavioral and molecular measures. Furthermore, we observed that for aged mice, the presence of a running wheel altered the amplitude of the spontaneous firing rate rhythm in the SCN in vitro. Following a shift of the LD cycle, both young and aged mice showed a change in rhythmicity properties of the mPER2::LUC oscillation of the SCN in vitro, and aged mice exhibited longer lasting internal desynchrony. Access to a running wheel alleviated some age-related changes in the circadian system. In an additional experiment, we replicated the effect of the running wheel, comparing behavioral and in vitro results from aged mice housed with or without a running wheel (>21 months, n = 8 per group, all examined 4 days after the shift). The impact of voluntary exercise on circadian rhythm properties in an aged animal is a novel finding and has implications for the health of older people living with environmentally induced circadian disruption

Paracellular permeability is increased by basal lipopolysaccharide in a primary culture of colonic epithelial cells; an effect prevented by an activator of Toll-like receptor-2

Lipopolysaccharide (LPS), which generally activates Toll-like receptor 4 (TLR4), is expressed on commensal colonic bacteria. In a number of tissues, LPS can act directly on epithelial cells to increase paracellular permeability. Such an effect in the colon would have an important impact on the understanding of normal homeostasis and of pathology. Our aim was to use a novel primary culture of colonic epithelial cells grown on Transwells to investigate whether LPS, or Pam(3)CSK( 4), an activator of TLR2, affected paracellular permeability. Consequently, [(14)C]-mannitol transfer and transepithelial electrical resistance (TEER) were measured. The preparation consisted primarily of cytokeratin-18 positive epithelial cells that produced superoxide, stained for mucus with periodic acid-Schiff reagent, exhibited alkaline phosphatase activity and expressed TLR2 and TLR4. Tight junctions and desmosomes were visible by transmission electron microscopy. Basally, but not apically, applied LPS from Escherichia coli increased the permeability to mannitol and to a 10-kDa dextran, and reduced TEER. The LPS from Helicobacter pylori increased paracellular permeability of gastric cells when applied either apically or basally, in contrast to colon cells, where this LPS was active only from the basal aspect. A pan-caspase inhibitor prevented the increase in caspase activity caused by basal E. coli LPS, and reduced the effects of LPS on paracellular permeability. Synthetic Pam(3)CSK(4) in the basal compartment prevented all effects of basal E. coli LPS. In conclusion, LPS applied to the base of the colonic epithelial cells increased paracellular permeability by a mechanism involving caspase activation, suggesting a process by which perturbation of the gut barrier could be exacerbated. Moreover, activation of TLR2 ameliorated such effects

Iron content in forage sorghum (Sorghum bicolor (L.) Moench) measured on different slit widths with atomic absorption spectrometry

Our objective was to know the right slit width for iron (Fe) concentration of forage sorghum, sorghum hybrid (Sorghum bicolor (L.) Moench), and also to discern which water treatment sludge (WTS) were good for ruminant's health with the feeding sorghum on the present study. The present experiment was carried out on a randomized block design with four treatments; Control, alum sludge compost, alum sludge + NPK (nitrogen, phosphorus, potassium fertilizers), alum sludge compost + NPK (nitrogen, phosphorus, potassium fertilizers). Sorghum hybrid was harvested, and iron content of it was analyzed with an atomic absorption spectrophotometer on background correction (BGC) mode. In order to analyze the iron (Fe) content of the sorghum with the spectrophotometer, three different slit widths conditions were used; 0.15, 0.20 and 0.25 nm. Absorbance and background values were obtained during the Fe analyses with the apparatus. When the background value is small, it is preferred for some trace metals’ analyses. Both (AM/BS) ratio (mean of the absorbance values<AM> to the standard deviation of back ground values<BS>) and (AS<standard deviation of the absorbance values>/BS) ratio, were larger on 0.25 nm slit than those on 0.15 and 0.20 nm slit, and, from our experiment, the condition seemed better on the 0.25 nm slit for the iron analysis with the spectrophotometer. Therefore, the sorghum hybrid grown on (Alum+NPK) and on (Compost only) might be dangerous for ruminants because of their higher values than 200 mg Fe/kg DM (dry matter).Key words: Absorbance, alum sludge, atomic absorption spectrophotometer, background, forage sorghum hybrid, iron, slit

Microguards and micromessengers of the genome

The regulation of gene expression is of fundamental importance to maintain organismal function and integrity and requires a multifaceted and highly ordered sequence of events. The cyclic nature of gene expression is known as ‘transcription dynamics’. Disruption or perturbation of these dynamics can result in significant fitness costs arising from genome instability, accelerated ageing and disease. We review recent research that supports the idea that an important new role for small RNAs, particularly microRNAs (miRNAs), is in protecting the genome against short-term transcriptional fluctuations, in a process we term ‘microguarding’. An additional emerging role for miRNAs is as ‘micromessengers’—through alteration of gene expression in target cells to which they are trafficked within microvesicles. We describe the scant but emerging evidence that miRNAs can be moved between different cells, individuals and even species, to exert biologically significant responses. With these two new roles, miRNAs have the potential to protect against deleterious gene expression variation from perturbation and to themselves perturb the expression of genes in target cells. These interactions between cells will frequently be subject to conflicts of interest when they occur between unrelated cells that lack a coincidence of fitness interests. Hence, there is the potential for miRNAs to represent both a means to resolve conflicts of interest, as well as instigate them. We conclude by exploring this conflict hypothesis, by describing some of the initial evidence consistent with it and proposing new ideas for future research into this exciting topic

Treatment patterns and clinical outcomes for patients with de novo versus recurrent HER2-positive metastatic breast cancer

Improvements in screening and adjuvant therapy for breast cancer are associated with decreased recurrence, which may have the effect of increasing the proportion of patients presenting with first-line de novo versus recurrent metastatic breast cancer (MBC). Here, we describe and compare patients with de novo versus recurrent human epidermal growth factor 2 (HER2)-positive MBC. registHER was a prospective observational cohort study (late 2003–early 2006) of 1,023 patients with HER2-positive MBC. Baseline characteristics, treatment patterns, and clinical outcomes were examined in patients with newly diagnosed de novo (n = 327) compared with recurrent HER2-positive MBC after prior treatment for early-stage disease (n = 674). Patients with de novo HER2-positive MBC were less likely to have lung metastases, more likely to have lymph node, bone, and/or liver metastases and >4 sites of metastases and more likely to receive combined or concurrent chemotherapy and hormonal therapy with or without trastuzumab than those with recurrent HER2-positive MBC. Median follow-up was 29 months. Median progression-free survival was 12.1 versus 9.3 months [hazard ratio = 0.716 (95 % confidence interval (CI) 0.617–0.831)], and overall survival was 41.7 versus 32.8 months [hazard ratio = 0.766 (95 % CI 0.633–0.928)] for patients with de novo versus recurrent HER2-positive MBC, respectively. Patients with recurrent HER2-positive MBC had similar outcomes regardless of whether they received prior adjuvant therapy, excluding hormonal therapy. Despite presenting with more advanced-stage disease and higher tumor burdens, patients with de novo HER2-positive MBC have more favorable clinical outcomes than those with recurrent HER2-positive MBC. These differences may be due to effects of prior drug exposure and could have implications for designing and interpreting clinical trials