Experimental and Computational Insights into the Overall Water Splitting Reaction by the Fe-Co-Ni-P Electrocatalyst.

Nonprecious transition-metal phosphides (TMPs) are versatile materials with tunable electronic and structural properties that could be promising as catalysts for energy conversion applications. Despite the facts, TMPs are not explored thoroughly to understand the chemistry behind their rich catalytic properties for the water splitting reaction. Herein, spiky ball-shaped monodispersed TMP nanoparticles composed of Fe, Co, and Ni are developed and used as efficient electrocatalysts for hydrogen and oxygen evolution reaction (HER, OER), and overall water splitting in alkaline medium; and their surface chemistry was explored to understand the reaction mechanism. The optimized Fe0.5CoNi0.5P catalyst shows attractive activities of HER and OER with low overpotentials and Tafel slopes, and with high mass activities, turnover frequencies, and exchange current densities. When applied to overall water splitting, the electrolyzer Fe0.5CoNi0.5P||Fe0.5CoNi0.5P cell can reach a 10 mA cm-2 current density at cell voltages of only 1.52 and 1.56 V in 1.0 M and 30 wt % KOH, respectively, much lower than those of commercial IrO2||Pt/C. The optimized electrolyzer with sizable numbers of chemically active sites exhibits superior durability up to 70 h and 5000 cycles in 1.0 M KOH and can attain a current density as high as 1000 mA cm-2, showing a class of efficient bifunctional electrocatalysis. Experimental and density functional theory-based mechanistic analyses reveal that surface reconstruction takes place in the presence of KOH to form the TMP precatalyst, which results in high coverage of oxygen active species for the OER with a low apparent activation energy (Ea) for conversion of *OOH to O2. These also evidenced the thermoneutral adsorption of H* for the efficient HER half-reaction.

A New Lignan from Annona squamosa L. (Annonaceae) Demonstrates Vasorelaxant Effects In Vitro.

Esquamosan, a new furofuran lignan, has been isolated by bio-guided assays from the methanolic extract of the leaves of Annona squamosa L., and its structure was elucidated by spectroscopic methods. Esquamosan inhibited the rat aortic ring contraction evoked by phenylephrine in a concentration-dependent manner and showed an inhibitory effect on vasocontraction of the depolarized aorta with high-concentration potassium. The vasorelaxant effect by esquamosan could be attributed mainly to the inhibition of calcium influx from extracellular space through voltage-dependent calcium channels or receptor-operated Ca2+ channels and also partly mediated through the increased release of NO from endothelial cells. The ability of esquamosan to modify the vascular reactivity of rat aortic rings incubated with high glucose (D-glucose 55 mM) was then evaluated, and this furofuran lignan reverted the endothelium-dependent impairment effect of high glucose in rat aortic rings. The antioxidant capacity of esquamosan was assessed using DPPH and FRAP assays. Esquamosan exhibited a similar antioxidant capacity compared to ascorbic acid, which was used as a positive control. In conclusion, this lignan showed a vasorelaxant effect, free radical scavenging capacity, and potential reductive power, suggesting its potential beneficial use to treat complex cardiometabolic diseases due to free radical-mediated diseases and its calcium antagonist effect.

Microproteins: Overlooked regulators of physiology and disease.

Ongoing efforts to generate a complete and accurate annotation of the genome have revealed a significant blind spot for small proteins (<100 amino acids) originating from short open reading frames (sORFs). The recent discovery of numerous sORF-encoded proteins, termed microproteins, that play diverse roles in critical cellular processes has ignited the field of microprotein biology. Large-scale efforts are currently underway to identify sORF-encoded microproteins in diverse cell-types and tissues and specialized methods and tools have been developed to aid in their discovery, validation, and functional characterization. Microproteins that have been identified thus far play important roles in fundamental processes including ion transport, oxidative phosphorylation, and stress signaling. In this review, we discuss the optimized tools available for microprotein discovery and validation, summarize the biological functions of numerous microproteins, outline the promise for developing microproteins as therapeutic targets, and look forward to the future of the field of microprotein biology.

Biorefinery and sustainability for the production of biofuels and value-added products: A trends analysis based on network and patent analysis.

Biorefineries are modern mechanisms used for producing value-added products and biofuels from different biomass sources. However, a crucial challenge is to achieve a sustainable model for their adequate implementation. Challenges related to technical efficiency and economic feasibility are two of the most relevant problems. Therefore, the present study sought to determine the current trends in basic research and technological development around biorefining and sustainability. We carried out a co-occurrence analysis and a patent analysis using data obtained from the Scopus and Lens databases to provide a general overview of the current state of this area of knowledge. The co-occurrence analysis intends to provide an overview of biorefining and sustainability based on terms associated with these two concepts as a starting point to determine the progress and existing challenges of the field. The results of the patent analysis consisted in identifying the main technological sectors, applicants, and territories where inventions associated with biorefining are registered. The analysis of the information showed that bioeconomy, techno-economic aspects, circular economy, technical issues associated with biomass production, and biofuels represent the focal point of basic research in a wide range of disciplines. Technology development is focused on fermentation, enzymes, and microorganisms, among other areas, which shows the validity of these traditional techniques in addressing the problems faced by the bioeconomy. This scenario shows that developed economies are the driving force behind this area of knowledge and that the PCT system is fundamental for the protection and commercialization of these inventions in places different from where they originated. Furthermore, the challenge lies in learning to work in alternative and complementary technological sectors, beyond microbiology and enzyme applications, in pursuit of the sector's technical and economic feasibility.

Dwarf Open Reading Frame (DWORF) Gene Therapy Ameliorated Duchenne Muscular Dystrophy Cardiomyopathy in Aged mdx Mice.

Background Cardiomyopathy is a leading health threat in Duchenne muscular dystrophy (DMD). Cytosolic calcium upregulation is implicated in DMD cardiomyopathy. Calcium is primarily removed from the cytosol by the sarcoendoplasmic reticulum calcium ATPase (SERCA). SERCA activity is reduced in DMD. Improving SERCA function may treat DMD cardiomyopathy. Dwarf open reading frame (DWORF) is a recently discovered positive regulator for SERCA, hence, a potential therapeutic target. Methods and Results To study DWORF's involvement in DMD cardiomyopathy, we quantified DWORF expression in the heart of wild-type mice and the mdx model of DMD. To test DWORF gene therapy, we engineered and characterized an adeno-associated virus serotype 9-DWORF vector. To determine if this vector can mitigate DMD cardiomyopathy, we delivered it to 6-week-old mdx mice (6×1012 vector genome particles/mouse) via the tail vein. Exercise capacity, heart histology, and cardiac function were examined at 18 months of age. We found DWORF expression was significantly reduced at the transcript and protein levels in mdx mice. Adeno-associated virus serotype 9-DWORF vector significantly enhanced SERCA activity. Systemic adeno-associated virus serotype 9-DWORF therapy reduced myocardial fibrosis and improved treadmill running, electrocardiography, and heart hemodynamics. Conclusions Our data suggest that DWORF deficiency contributes to SERCA dysfunction in mdx mice and that DWORF gene therapy holds promise to treat DMD cardiomyopathy.

1H NMR global diatropicity in copper hydride complexes.

Understanding the magnetic response of electrons in nanoclusters is essential to interpret their NMR spectra thereby providing guidelines for their synthesis towards various target applications. Here, we consider two copper hydride clusters that have applications in hydrogen storage and release under standard temperature and pressure. Through Born-Oppenheimer molecular dynamics simulations, we study dynamics effects and their contributions to the NMR peaks. Finally, we examine the electrons' magnetic response to an applied external magnetic field using the gauge-including magnetically induced currents theory. Local diatropic currents are generated in both clusters but an interesting global diatropic current also appears. This diatropic current has contributions from three µ3-H hydrides and six Cu atoms that form a chain together with three S atoms from the closest ligands resulting in a higher shielding of these hydrides' 1H NMR response. This explains the unusual upfield chemical shift compared to the common downfield shift in similarly coordinated hydrides both observed in previous experimental reports.

An Integrated Approach for Microprotein Identification and Sequence Analysis.

Next-generation sequencing (NGS) has propelled the field of genomics forward and produced whole genome sequences for numerous animal species and model organisms. However, despite this wealth of sequence information, comprehensive gene annotation efforts have proven challenging, especially for small proteins. Notably, conventional protein annotation methods were designed to intentionally exclude putative proteins encoded by short open reading frames (sORFs) less than 300 nucleotides in length to filter out the exponentially higher number of spurious noncoding sORFs throughout the genome. As a result, hundreds of functional small proteins called microproteins (<100 amino acids in length) have been incorrectly classified as noncoding RNAs or overlooked entirely. Here we provide a detailed protocol to leverage free, publicly available bioinformatic tools to query genomic regions for microprotein-coding potential based on evolutionary conservation. Specifically, we provide step-by-step instructions on how to examine sequence conservation and coding potential using Phylogenetic Codon Substitution Frequencies (PhyloCSF) on the user-friendly University of California Santa Cruz (UCSC) Genome Browser. Additionally, we detail steps to efficiently generate multiple species alignments of identified microprotein sequences to visualize amino acid sequence conservation and recommend resources to analyze microprotein characteristics, including predicted domain structures. These powerful tools can be used to help identify putative microprotein-coding sequences in noncanonical genomic regions or to rule out the presence of a conserved coding sequence with translational potential in a noncoding transcript of interest.

Analysis of wavelength-scale 1D depth-dependent refractive-index gradients at an interface by their effects on the internal reflectance near the critical angle.

Light's internal reflectivity near a critical angle is very sensitive to the angle of incidence and the optical properties of the external medium near the interface. Novel applications in biology and medicine of subcritical internal reflection are being pursued. In many practical situations, the refractive index of the external medium may vary with respect to its bulk value due to different physical phenomena at surfaces. Thus, there is a pressing need to understand the effects of a refractive-index gradient at a surface for near-critical-angle reflection. In this work, we investigate theoretically the reflectivity near the critical angle at an interface with glass assuming the external medium has a continuous depth-dependent refractive index. We present graphs of the internal reflectivity as a function of the angle of incidence, which exhibit the effects of a refractive-index gradient at the interface. We analyze the behavior of the reflectivity curves before total internal reflection is achieved. Our results provide insight into how one can recognize the existence of a refractive-index gradient at the interface and shed light on the viability of characterizing it.

Cubic aromaticity in ligand-stabilized doped Au superatoms.

The magnetic response of valence electrons in doped gold-based M@Au8L8 q superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L = PPh3; and q = 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) in the framework of the auxiliary density functional theory. The studied systems include 24 different combinations of the dopant, total cluster charge, and cluster structure (cubic-like or oblate). The magnetically induced currents (both diatropic and paratropic) are shown to be sensitive to the atomic structure of clusters, the number of superatomic electrons, and the chemical nature of the dopant metal. Among the cubic-like structures, the strongest aromaticity is observed in Pd- and Pt-doped M@Au8L8 0 clusters. Interestingly, Pd- and Pt-doping increases the aromaticity as compared to a similar all-gold eight-electron system Au9L8 +1. With the recent implementation of the GIMIC in the deMon2k code, we investigated the aromaticity in the cubic and butterfly-like M@Au8 core structures, doped with a single M atom from periods 5 and 6 of groups IX-XII. Surprisingly, the doping with Pd and Pt in the cubic structure increases the aromaticity compared to the pure Au case not only near the central atom but encompassing the whole metallic core, following the aromatic trend Pd > Pt > Au. These doped (Pd, Pt)@Au8 nanoclusters show a closed shell 1S21P6 superatom electronic structure corresponding to the cubic aromaticity rule 6n + 2.