Cofactor-independent C-C bond cleavage reactions catalyzed by the AlpJ family of oxygenases in atypical angucycline biosynthesis.

Biosynthesis of atypical angucyclines involves unique oxidative B-ring cleavage and rearrangement reactions, which are catalyzed by AlpJ-family oxygenases, including AlpJ, JadG, and GilOII. Prior investigations established the essential requirement for FADH2/FMNH2 as cofactors when utilizing the quinone intermediate dehydrorabelomycin as a substrate. In this study, we unveil a previously unrecognized facet of these enzymes as cofactor-independent oxygenases when employing the hydroquinone intermediate CR1 as a substrate. The enzymes autonomously drive oxidative ring cleavage and rearrangement reactions of CR1, yielding products identical to those observed in cofactor-dependent reactions of AlpJ-family oxygenases. Furthermore, the AlpJ- and JadG-catalyzed reactions of CR1 could be quenched by superoxide dismutase, supporting a catalytic mechanism wherein the substrate CR1 reductively activates molecular oxygen, generating a substrate radical and the superoxide anion O2 •-. Our findings illuminate a substrate-controlled catalytic mechanism of AlpJ-family oxygenases, expanding the realm of cofactor-independent oxygenases. Notably, AlpJ-family oxygenases stand as a pioneering example of enzymes capable of catalyzing oxidative reactions in either an FADH2/FMNH2-dependent or cofactor-independent manner.

Electron transfer at the heterojunction interface of CoP/MoS2 for efficient electrocatalytic hydrogen evolution reaction.

Modulating the electronic states of electrocatalysts is critical for achieving efficient hydrogen evolution reaction (HER). However, how to develop electrocatalysts with superior electronic states is an urgent challenge that must be addressed. Herein, we prepared the CoP/MoS2 heterojunction with a microsphere morphology consisting of thin nanosheets using a facile two-step method. The catalyst's ultrathin nanosheet structure not only provides an extensive surface area for exposing active sites, but it also enables ion transport and bubble release. Electron transfer occurs between CoP and MoS2, optimizing the heterojunction's charge distribution and enhancing the intermediates' adsorption capabilities. As a result, the CoP/MoS2 heterojunction exhibits outstanding electrocatalytic hydrogen evolution activity with an overpotential of only 88 mV at a current density of 10 mA cm-2, which exceeds both the sulfide heterojunction Co9S8/MoS2 and the phosphide heterojunction CoP/CoMoP2. The experimental results and DFT calculation results show that the former has stronger synergistic effects and higher HER activity. This work sheds light on the exploration of efficient heterojunction electrocatalysts with excellent electronic structures.

An in situ phase transformation induced mesoporous heterointerface for the alkaline hydrogen evolution reaction.

The phase structure of a catalyst plays a crucial role in determining the catalytic activity. In this study, a facile phosphorization process is employed to achieve the in situ phase transformation from single-phase Co3O4 to CoO/CoP hybrid phases. Characterization techniques, including XRD, BET, SEM, and TEM, confirm the retention of the mesoporous nature during the phase transformation, forming porous CoO/CoP heterointerfaces. Strong charge transfer is observed across the CoO/CoP heterointerface, indicating a robust interaction between the hybrid phases. The CoO/CoP hybrid exhibits significantly enhanced catalytic activity for the alkaline hydrogen evolution reaction (HER) compared to pristine Co3O4. Density Functional Theory (DFT) calculations reveal that the elimination of the band gap in the spin-down band of Co in CoO/CoP contributes to the observed high HER activity. The findings highlight the potential of CoO/CoP hybrids as efficient catalysts for HER, and contribute to the advancement of catalyst design for sustainable energy applications.

CoPS/Co4S3 Heterojunction with Highly Exposed Active Sites and Dual-site Synergy for Effective Hydrogen Evolution Reactions.

Cobalt phosphosulphide (CoPS) has recently been recognized as a potentially effective electrocatalyst for the hydrogen evolution reaction (HER). However, there have been no research on the design of CoPS-based heterojunctions to boost their HER performance. Herein, CoPS/Co4S3 heterojunction was prepared by phosphating treatment based on defect-rich flower-like Co1-xS precursors. The high specific surface area of nanopetals, together with the heterojunction structure with inhomogeneous strain, exposes more active sites in the catalyst. The electronic structure of the catalyst is reconfigured as a result of the interfacial interactions, which promote the catalyst's ability to adsorb hydrogen and conduct electricity. The synergistic effect of the Co and S dual-site further enhance the catalytic activity. The catalyst has overpotentials of 61 and 70 mV to attain a current density of 10 mA cm-2 in acidic and alkaline media, respectively, which renders it competitive with previously reported analogous catalysts. This work proposes an effective technique for constructing transition metal phosphosulfide heterojunctions, as well as the development of an efficient HER electrocatalyst.

Lattice Defects and Electronic Modulation of Flower-Like Zn3 In2 S6 Promote Photocatalytic Degradation of Multiple Antibiotics.

Photocatalysis is an effective technique to remove antibiotic residues from aquatic environments. Typical metal sulfides like Zn3 In2 S6 have been applied to a wide range of photocatalytic applications. However, there are currently no readily accessible methods to increase its antibiotic-degrading activity. Here, a facile hydrothermal approach is developed for the preparation of flower-like Zn3 In2 S6 with tunable sulfur lattice defects. Photogenerated carriers can be separated and transferred more easily when there is an adequate amount of lattice defects. Moreover, lattice defect-induced electronic modulation enhances light utilization and adsorption properties. The modified Zn3 In2 S6 demonstrates outstanding photocatalytic degradation activity for levofloxacin, ofloxacin, and tetracycline. This work sheds light on exploring metal sulfides with sulfur lattice defects for enhancing photocatalytic activity.

Multi-d Electron Synergy in LaNi1-x Cox Ru Intermetallics Boosts Electrocatalytic Hydrogen Evolution.

Despite the fact that d-band center theory links the d electron structure of transition metals to their catalytic activity, it is yet unknown how the synergistic effect of multi-d electrons impacts catalytic performance. Herein, novel LaNi1-x Cox Ru intermetallics containing 5d, 4d, and 3d electrons were prepared. In these compounds, the 5d orbital of La transfers electrons to the 4d orbital of Ru, which provides adsorption sites for H*. The 3d orbitals of Ni and Co interact with the 5d and 4d orbitals to generate an anisotropic electron distribution, which facilitates the adsorption and desorption of OH*. The synergistic effect of multi-d electrons ensures efficient catalytic activity. The optimized LaNi0.5 Co0.5 Ru has an overpotential of 43mV at 10 mA cm-2 for alkaline electrocatalytic hydrogen evolution reaction. Beyond offering a variety of new electrocatalysts, this work reveals the multi-d electron synergy in promoting catalytic reaction.

Nontrivial Topological Surface States in Ru3 Sn7 toward Wide pH-Range Hydrogen Evolution Reaction.

Nontrivial topological surface states (TSSs), which possess extraordinary carrier mobility and are protected by the bulk symmetry, have emerged as an innovative platform to search for efficient electrocatalysts toward hydrogen evolution reaction (HER). Here, a Sn-based nontrivial metal Ru3 Sn7 is prepared using electrical arc melting method. The results indicate that the (001) crystal family of Ru3 Sn7 possesses nontrivial TSSs with linear dispersion relation and large nontrivial energy window. Experimental and theoretical results demonstrate that nontrivial TSSs of Ru3 Sn7 can significantly boost charge transfer kinetics and optimize adsorption of hydrogen intermediates due to bulk symmetry-protected band structures. As expected, nontrivial Ru3 Sn7 exhibits superior HER activity to Ru, Pt/C, and trivial counterparts (e.g., Ru2 Sn3 , IrSn2 , and Rh3 Sn2 ) with higher ratios of noble metals. Furthermore, the wide pH-range activity of topologically nontrivial Ru3 Sn7 implies the robustness of its TSSs against pH variation during the HER. These findings provide a promising approach to the rational design of topologically nontrivial metals as highly efficient electrocatalysts.

Charge Redistribution of Co9S8/MoS2 Heterojunction Microsphere Enhances Electrocatalytic Hydrogen Evolution.

The electrocatalytic hydrogen evolution activity of transition metal sulfide heterojunctions are significantly increased when compared with that of a single component, but the mechanism behind the performance enhancement and the preparation of catalysts with specific morphologies still need to be explored. Here, we prepared a Co9S8/MoS2 heterojunction with microsphere morphology consisting of thin nanosheets using a facile two-step method. There is electron transfer between the Co9S8 and MoS2 of the heterojunction, thus realizing the redistribution of charge. After the formation of the heterojunction, the density of states near the Fermi surface increases, the d-band center of the transition metal moves downward, and the adsorption of both water molecules and hydrogen by the catalyst are optimized. As a result, the overpotential of Co9S8/MoS2 is superior to that of most relevant electrocatalysts reported in the literature. This work provides insight into the synergistic mechanisms of heterojunctions and their morphological regulation.

Integrated bioinformatic analyses investigate macrophage-M1-related biomarkers and tuberculosis therapeutic drugs.

Tuberculosis (TB) is a common infectious disease linked to host genetics and the innate immune response. It is vital to investigate new molecular mechanisms and efficient biomarkers for Tuberculosis because the pathophysiology of the disease is still unclear, and there aren't any precise diagnostic tools. This study downloaded three blood datasets from the GEO database, two of which (GSE19435 and 83456) were used to build a weighted gene co-expression network for searching hub genes associated with macrophage M1 by the CIBERSORT and WGCNA algorithms. Furthermore, 994 differentially expressed genes (DEGs) were extracted from healthy and TB samples, four of which were associated with macrophage M1, naming RTP4, CXCL10, CD38, and IFI44. They were confirmed as upregulation in TB samples by external dataset validation (GSE34608) and quantitative real-time PCR analysis (qRT-PCR). CMap was used to predict potential therapeutic compounds for tuberculosis using 300 differentially expressed genes (150 downregulated and 150 upregulated genes), and six small molecules (RWJ-21757, phenamil, benzanthrone, TG-101348, metyrapone, and WT-161) with a higher confidence value were extracted. We used in-depth bioinformatics analysis to investigate significant macrophage M1-related genes and promising anti-Tuberculosis therapeutic compounds. However, more clinical trials were necessary to determine their effect on Tuberculosis.

Phosphorus-modified cobalt single-atom catalysts loaded on crosslinked carbon nanosheets for efficient alkaline hydrogen evolution reaction.

Efficient and low-cost transition metal single-atom catalysts (TMSACs) for hydrogen evolution reaction (HER) have been recognized as research hotspots recently with advances in delivering good catalytic activity without noble metals. However, the high-cost complex preparation of TMSACs and insufficient stability limited their practical applications. Herein, a simple top-down pyrolysis approach to obtain P-modified Co SACs loaded on the crosslinked defect-rich carbon nanosheets was introduced for alkaline hydrogen evolution, where Co atoms are locally confined before pyrolysis to prevent aggregation. Thereby, the abundant defects and the unsaturated coordination formed during the pyrolysis significantly improved the stability of the monatomic structure and reduced the reaction barrier. Furthermore, the synergy between cobalt atoms and phosphorus atoms was established to optimize the decomposition process of water molecules, which delivers the key to promoting the slow reaction kinetics of alkaline HER. As the result, the cobalt SAC exhibited excellent catalytic activity and stability for alkaline HER, with overpotentials of 70 mV and 192 mV at current densities of -10 mA cm-2 and -100 mA cm-2, respectively.

Construction of Cobalt Molybdenum Diselenide Three-phase Heterojunctions for Electrocatalytic Hydrogen Evolution in Acid Medium.

Molybdenum diselenide and cobalt diselenide have been commonly implemented in electrocatalytic hydrogen evolution reaction (HER). However, there have been few research on the creation of their three-phase heterojunctions and the associated HER process. Herein, we constructed a three-phase heterostructure sample consisting of orthorhombic CoSe2 , cubic CoSe2 and MoSe2 and we investigated its HER performance. The sample shows microsphere morphology composed of nanosheets with interfacial interactions between the components. It possesses an overpotential of -136 mV at -10 mA cm-2 in acid medium, which is superior to that of single component and most two-phase heterostructures. Especially, the overpotential at -200 mA cm-2 is smaller than that of Pt/C. The excellent performance can be attributed to the d-orbital upshift of the Co active sites due to charge redistribution between the three-phase heterojunction and the optimization of the hydrogen free energy. This work provides inspiration for exploring the application of other multi-component heterojunctions in electrocatalytic hydrogen evolution.

Identification of QTLs for Heat Tolerance at the Flowering Stage Using Chromosome Segment Substitution Lines in Rice.

High temperature is a major stress in rice production. Although considerable progress has been made in investigating heat tolerance (HT) in rice, the genetic basis of HT at the heading stage remains largely unknown. In this study, a novel set of chromosome segment substitution lines (CSSLs) consisting of 113 lines derived from a heat-resistant indica variety N22 and a heat-sensitive indica variety 9311 was developed and used for the analysis of the genetic basis of HT. The heat sensitivity index (HSI) calculated based on seed-setting rates under natural and high-temperature environments was used to evaluate the influence of HT at the rice heading stage. In total, five quantitative trait loci (QTLs) associated with HT were detected based on seed-setting rate (SSR) evaluation; these were named qSSR6-1, qSSR7-1, qSSR8-1, qSSR9-1 and qSSR11-1 located on chromosomes 6, 7, 8, 9 and 11, respectively. Heat-tolerant alleles of the QTLs were all derived from N22. Among them, qSSR9-1 overlapped with QTLs identified previously, while the remaining QTLs were found novel. In particular, qSSR7-1 explained a high phenotypic variation of 26.35% with a LOD score of 10.75, thus deserved to be further validated. These findings will increase our understanding of the genetic mechanism underlying HT and facilitate the breeding of heat-tolerant rice varieties.

Interlayer Spacing Regulation of Molybdenum Selenide Promotes Electrocatalytic Hydrogen Evolution in Alkaline Media.

The construction of heterostructures is a versatile tactic to enhance catalytic activity. However, it is still elusive to realize the modulation of the interlayer spacing in this way to further improve the performance. Here, strong interfacial coupling between CoSe2 and MoSe2 by constructing CoSe2 /MoSe2 heterostructures is achieved. The interlayer spacing of MoSe2 is compressed by 0.3 Å. The enhanced charge transfer is validated by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. Coupled with the morphology of hollow microtubes, which can facilitate the exposure of active sites, CoSe2 /MoSe2 heterostructures reported here exhibit high activity (119 mV at 10 mA cm-2 ) and excellent stability with small degradation after 50 h operation, surpassing other analogous powdered electrocatalysts. This work sheds light on the importance of tuning the interlayer spacing to improve electrocatalytic activity.

Highly Active Si Sites Enabled by Negative Valent Ru for Electrocatalytic Hydrogen Evolution in LaRuSi.

The discovery and identification of novel active sites are paramount for deepening the understanding of the catalytic mechanism and driving the development of remarkable electrocatalysts. Here, we reveal that the genuine active sites for the hydrogen evolution reaction (HER) in LaRuSi are Si sites, not the usually assumed Ru sites. Ru in LaRuSi has a peculiar negative valence state, which leads to strong hydrogen binding to Ru sites. Surprisingly, the Si sites have a Gibbs free energy of hydrogen adsorption that is near zero (0.063 eV). The moderate adsorption of hydrogen on Si sites during the HER process is also validated by in situ Raman analysis. Based on it, LaRuSi exhibits an overpotential of 72 mV at 10 mA cm-2 in alkaline media, which is close to the benchmark of Pt/C. This work sheds light on the recognition of real active sites and the exploration of innovative silicide HER electrocatalysts.

Magnetic lump motion in saturated ferromagnetic films.

In this paper, we study in detail the nonlinear propagation of a magnetic soliton in a ferromagnetic film. The sample is magnetized to saturation by an external field perpendicular to film plane. A generalized (2+1)-dimensional short-wave asymptotic model is derived. The bilinearlike forms of this equation are constructed and exact magnetic line soliton solutions are exhibited. It is observed that a series of stable lumps can be generated by an unstable magnetic soliton under Gaussian disturbance. Such magnetic lumps are highly stable and can maintain their shapes and velocities during evolution or collision. The interaction between lump and magnetic solitons, as well as the interaction between two lumps, are numerically investigated. We further discuss the nonlinear motion of lumps in ferrites with Gilbert damping and inhomogeneous exchange effects. The results show that the Gilbert-damping effects make the amplitude and velocity of the magnetic lump decay exponentially during propagation. And the shock waves are generated from a lump when quenching the strength of inhomogeneous exchange.

Crystalline-Amorphous Interfaces Coupling of CoSe2 /CoP with Optimized d-Band Center and Boosted Electrocatalytic Hydrogen Evolution.

Amorphous and heterojunction materials have been widely used in the field of electrocatalytic hydrogen evolution due to their unique physicochemical properties. However, the current used individual strategy still has limited effects. Hence efficient tailoring tactics with synergistic effect are highly desired. Herein, the authors have realized the deep optimization of catalytic activity by a constructing crystalline-amorphous CoSe2 /CoP heterojunction. Benefiting from the strong electronic coupling at the interfaces, the d-band center of the material moves further down compared to its crystalline-crystalline counterpart, optimizing the valence state and the H adsorption of Co and lowering the kinetic barrier of hydrogen evolution reaction (HER). The heterojunction shows an overpotential of 65 mV to drive a current density of 10 mA cm-2 in the acidic medium. Besides, it also shows competitive properties in both neutral and basic media. This work provides inspiration for optimizing the catalytic activity through combining a crystalline and amorphous heterojunction, which can be implemented for other transition metal compound electrocatalysts.

Selecting Hub Genes and Predicting Target Genes of microRNAs in Tuberculosis via the Bioinformatics Analysis.

Tuberculosis (TB) is the world's most prevalently infectious disease. Molecular mechanisms behind tuberculosis remain unknown. microRNA (miRNA) is involved in a wide variety of diseases. To validate the significant genes and miRNAs in the current sample, two messenger RNA (mRNA) expression profile datasets and three miRNA expression profile datasets were downloaded from the Gene Expression Omnibus (GEO) database. The differentially expressed (DE) genes (DEGs) and miRNAs (DE miRNAs) between healthy and TB patients were filtered out. Enrichment analysis was executed, and a protein-protein interaction (PPI) network was developed to understand the enrich pathways and hub genes of TB. Additionally, the target genes of miRNA were predicted and overlapping target genes were identified. We studied a total of 181 DEGs (135 downregulated and 46 upregulated genes) and two DE miRNAs (2 downregulated miRNAs) from two gene profile datasets and three miRNA profile datasets, respectively. 10 hub genes were defined based on high degree of connectivity. A PPI network's top module was constructed. The 23 DEGs identified have a significant relationship with miRNAs. 25 critically significant Gene ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways were discovered. The detailed study revealed that, in tuberculosis, the DE miRNA and DEGs form an interaction network. The identification of novel target genes and main pathways would aid with our understanding of miRNA's function in tuberculosis progression.

Laser ablation in air and its application in catalytic water splitting and Li-ion battery.

Pulse laser has been widely used in both fundamental science and practical technologies. In this perspective, we highlight the employment of pulse laser ablation in air (LAA) in energy-related catalytic reactions. With LAA, samples are directly ablated in ambient air, which makes this technology facile to conduct. Materials can be modified by LAA in multiple aspects, such as morphology modulation, heterojunction fabrication, or defects engineering, which are desired features for energy-related catalytic reactions. We begin this perspective with a brief introduction of this technology, including the mechanism, the experimental setup, and the characteristic of laser-ablated materials. The recent works utilizing LAA are then summarized to prove the promising prospects of LAA in the energy field. Finally, several opportunities about the future usage of LAA are proposed and discussed.

Systematic characterization of chemical constituents in Mahuang decoction by UHPLC tandem linear ion trap-Orbitrap mass spectrometry coupled with feature-based molecular networking.

Comprehensive characterization of traditional Chinese medicine prescriptions has long been a hurdle due to the chemical complexity and the lack of analytical tools. Mahuang decoction is a well-known traditional Chinese medicine prescription widely used for sweating and relieving the exterior, relieving cough and asthma, but it was insufficiently chemically scrutinized. In this study, the chemical component information of Mahuang decoction was investigated by ultrahigh-performance liquid chromatography tandem linear ion trap-Orbitrap mass spectrometry. A new data processing tool, feature-based molecular networking, was introduced for grouping and elucidating the compounds. In this way, 156 chemical components were identified or tentatively characterized, including alkaloids, triterpenoid saponins, flavanone-O-glycosides, flavone-C-glycosides, and procyanidins. Thus, this research provides a solid foundation for further development of Mahuang decoction, and the adopted method is expected to be applied to other traditional Chinese medicine prescriptions.

Reversed Active Sites Boost the Intrinsic Activity of Graphene-like Cobalt Selenide for Hydrogen Evolution.

Optimizing the hydrogen adsorption Gibbs free energy (ΔGH ) of active sites is essential to improve the overpotential of the electrocatalytic hydrogen evolution reaction (HER). We doped graphene-like Co0.85 Se with sulfur and found that the active sites are reversed (from cationic Co sites to anionic S sites), which contributed to an enhancement in electrocatalytic HER performance. The optimal S-doped Co0.85 Se composite has an overpotential of 108 mV (at 10 mA cm-2 ) and a Tafel slope of 59 mV dec-1 , which exceeds other reported Co0.85 Se-based electrocatalysts. The doped S sites have much higher activity than the Co sites, with a hydrogen adsorption Gibbs free energy (ΔGH ) close to zero (0.067 eV), which reduces the reaction barrier for hydrogen production. This work provides inspiration for optimizing the intrinsic HER activity of other related transition metal chalcogenides.