NiS/FeS binary nanoparticles confined in interconnected carbon framework with regulated pore structure enabled by citric acid for enhanced sodium storage properties.

Recently, pyrite iron disulfide (FeS) has emerged as a promising anode candidate for sodium-ion batteries (SIBs) due to its high theoretical capacity, affordability, non-toxicity and abundant resource in nature. However, the utilization of FeS still confronts the challenges of inferior rate capability and cycling instability for sodium storage, stemming from its low electronic conductivity and substantial volume changes during cycling. Herein, to address these obstacles, NiS/FeS binary nanoparticles encapsulated within a network of interconnected N-doped porous carbon framework (NiS/FeS@NPC) are prepared by a successive solid-state ball milling, carbonization and sulfurization strategy with coordination complex of nickel iron Prussian blue analogue (NiFe-PBA) as precursor.

Annonaceous acetogenins mimic AA005 targets mitochondrial trifunctional enzyme alpha subunit to treat obesity in male mice.

Obesity and related diseases pose a major health risk, yet current anti-obesity drugs inadequately addressing clinical needs. Here we show AA005, an annonaceous acetogenin mimic, resists obesity induced by high-fat diets and leptin mutations at non-toxic doses, with the alpha subunit of the mitochondrial trifunctional protein (HADHA) as a target identified through proteomics and in vitro validation. Pharmacokinetic analysis shows AA005 enriches in adipose tissue, prompting the creation of adipose-specific Hadha-deficient mice.

Quick Access to Protoberberine and Tetrahydroprotoberberine Derivatives/Analogues with One-Pot Sequential Isochromenylium-Mediated Annulation.

A one-pot access to the protoberberine and tetrahydroprotoberberine scaffold has been developed from easily available primary amine-functionalized -alkynylbenzaldehydes. The core skeleton of protoberberine was afforded via generation of isochromenylium by Ag(I) catalysis, subsequent cyclization to isoquinolinium, and final hydride reduction by a continuous operation procedure. The newly developed step-economic protocol shows excellent regio- and stereoselectivity and is capable of achieving those previously unavailable derivatives/analogues with electron-deficient substituents, providing a robust tool for medicinal investigations of protoberberines and derivatives.

Metal Coordination Complex Derived FeS Particles Embedded in N-doped Carbon Framework with Regulated Porous Structure Enabling High-Rate and Durable Sodium Storage.

Iron sulfides with high theoretical capacity confront the challenges of low rate capability and severe capacity fading for sodium storage, which are mainly caused by poor electron/ion transport kinetics and drastic volume fluctuations during cycling. Herein, to mitigate these obstacles, a multi-step synthetic tactic involving solvothermal, carbonization, and subsequent sulfurization is put forward for the construction of wire-like structure by confining FeS particles in porous N-doped carbon framework (denoted as FeS/PNC) using zinc iron nitrilotriacetate as template. By partially substituting Fe with Zn in the metal coordination complex, the porous structure of coordination complex derived carbon framework can be regulated through pore structure engineering of Zn nanodroplets.

Achieving High-Rate and Stable Sodium-Ion Storage by Constructing Okra-Like NiS/FeS@Multichannel Carbon Nanofibers.

Transition metal sulfides (TMSs) are considered as promising anode materials for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, the relatively low electrical conductivity, large volume variation, and easy aggregation/pulverization of active materials seriously hinder their practical application. Herein, okra-like NiS/FeS particles encapsulated in multichannel N-doped carbon nanofibers (NiS/FeS@MCNFs) are fabricated by a coprecipitation, electrospinning, and carbonization/sulfurization strategy.

3-Acyl-4-Pyranone as a Lysine Residue-Selective Bioconjugation Reagent for Peptide and Protein Modification.

Chemoselective protein modification plays extremely important roles in various biological, medical, and pharmaceutical investigations. Mimicking the mechanism of the chemoselective reaction between natural azaphilones and primary amines, this work successfully simplified the azaphilone scaffold into much simpler 3-acyl-4-pyranones. Examinations confirmed that these slim-size mimics perfectly kept the unique reactivity for selective conjugation with the primary amines including lysine residues of peptides and proteins.

Development of Cyclic ,-Aminal-Embedded Bis-tetrahydroisoquinoline Analogues as Potential DNA Alkylation Agents.

This work described a novel "functional hybrid" design for bis-tetrahydroisoquinoline (bis-THIQ) analogues as potential DNA alkylation agents by replacing the labile C21-carbinolamine on the bis-THIQ skeleton of ET-743 with a chemically stable cyclic ,-aminal functionality. anti-proliferation evaluation has proven that it is a successful approach to deliver new bis-THIQ analogues with common cytotoxicities, among which several exhibited sub-micromolar-range IC against the proliferation of human cancer cell lines A549, HepG2, and MDA-MB-231, respectively.

Isochromenylium/Isoquinolinium-Mediated One-Pot Annulation to Hexahydropyrazinoisoquinolines. Synthesis of Quinocarcinol.

A novel annulation protocol has been successfully developed in this work for the quick generation of 1,3,4,6,11,11a-hexahydro-2-pyrazino[1,2-]isoquinolines from easily accessible -alkynylbenzaldehydes. Various hexahydropyrazinoisoquinolines, including those previously unavailable with electron-deficient substituents, have been achieved via the newly developed continuously operational isochromenylium/isoquinolinium-mediated procedure. It also perfectly served as a key step to generate the basic skeleton in the new total synthesis of quinocarcinol, accompanied by the development and application of a direct late-stage stereoselective sp C-H hydroxymethylation.

Phosphodiesterase 5 and Arginase Inhibitory Activities of the Extracts from Some Members of Nelumbonaceae and Nymphaeaceae Families.

The objectives of this study were (1) to investigate the effect of extracts from some plants in the families Nelumbonaceae and Nymphaeaceae on phosphodiesterase 5 (PDE5) and arginase, which have been used in erectile dysfunction treatment, and (2) to isolate and identify the compounds responsible for such activities. The characterization and quantitative analysis of flavonoid constituents in the active extracts were performed by HPLC. Thirty-seven ethanolic extracts from different parts of plants in the genus and of Nymphaeaceae and genus of Nelumbonaceae were screened for PDE5 and arginase inhibitory activities.

Spatially Confined FeS Nanoparticles Anchored on a Porous Nitrogen-Doped Carbon Nanosheet Skeleton for High-Rate and Durable Sodium Storage.

Iron sulfides are widely explored as anodes of sodium-ion batteries (SIBs) owing to high theoretical capacities and low cost, but their practical application is still impeded by poor rate capability and fast capacity decay. Herein, for the first time, we construct highly dispersed FeS nanoparticles anchored on a porous N-doped carbon nanosheet (CN) skeleton (denoted as FeS/NC) with high conductivity and numerous active sites facile ion adsorption and thermal evaporation combined procedures coupled with a gas sulfurization treatment. Nanoscale design coupled with a conductive carbon skeleton can simultaneously mitigate the above obstacles to obtain enhanced structural stability and faster electrode reaction kinetics.

Comprehensive Survey of ChIP-Seq Datasets to Identify Candidate Iron Homeostasis Genes Regulated by Chromatin Modifications.

Vital biochemical reactions including photosynthesis to respiration require iron, which should be tightly regulated. Although increasing evidence reveals the importance of epigenetic regulation in gene expression and signaling, the role of histone modifications and chromatin remodeling in plant iron homeostasis is not well understood. In this study, we surveyed publicly available ChIP-seq datasets of Arabidopsis wild-type and mutants defective in key enzymes of histone modification and chromatin remodeling and compared the deposition of epigenetic marks on loci of genes involved in iron regulation.

Prussian Blue Analogue-Derived Fe-Doped CoS Nanoparticles Confined in Bayberry-like N-Doped Carbon Spheres as Anodes for Sodium-Ion Batteries.

Obvious volume change and the dissolution of polysulfide as well as sluggish kinetics are serious issues for the development of high performance metal sulfide anodes for sodium-ion batteries (SIBs), which usually result in fast capacity fading during continuous sodiation and desodiation processes. In this work, by utilizing a Prussian blue analogue as functional precursors, small Fe-doped CoS nanoparticles spatially confined in N-doped carbon spheres with rich porosity were synthesized through facile successive precipitation, carbonization, and sulfurization processes, leading to the formation of bayberry-like Fe-doped CoS/N-doped carbon spheres (Fe-CoS/NC). By introducing a suitable amount of FeCl in the starting materials, the optimal Fe-CoS/NC hybrid spheres with the designed composition and pore structure exhibited superior cycling stability (621 mA h g after 400 cycles at 1 A g) and improved the rate capability (493 mA h g at 5 A g).

Simplified hybrids of two anticancer bistetrahydroisoquinoline alkaloids ecteinascidin 743 and cribrostatin 4 and inhibitory activity against proliferation of cancer cells.

Ecteinascidin 743 is a famous marine drug used in anticancer treatments. In this work, a series of simplified hybrids/analogues have been synthesized by employing a newly developed chemistry that integrates the partial structural features of two anticancer bis-tetrahydroisoquinoline alkaloids ecteinascidin 743 and cribrostatin 4. The described Suzuki-coupling protocol enabled us to easily introduce variable functionalities at the C3 position of the basic skeleton of bis-tetrahydroisoquinoline alkaloids for the first time.

Enantioselective Total Synthesis of (+)-Sieboldine A and Analogues Thereof.

An 11-step enantioselective total synthesis of (+)-sieboldine A () has been accomplished from (5)-methylcyclohex-2-en-1-one (), in which an intramolecular ketone/ester reductive coupling followed by one-pot acidic treatment to quickly construct the unique oxa-spiroacetal and a TsOH-catalyzed displacement to directly form the characteristic -hydroxyazacyclononane ring successfully served as the key methodologies. Moreover, several full-skeleton analogues of were also synthesized on the basis of the advanced intermediates, and their inhibitory effects on electric eel acetylcholinesterase were examined.

Minireview: Chromatin-based regulation of iron homeostasis in plants.

Plants utilize delicate mechanisms to effectively respond to changes in the availability of nutrients such as iron. The responses to iron status involve controlling gene expression at multiple levels. The regulation of iron deficiency response by a network of transcriptional regulators has been extensively studied and recent research has shed light on post-translational control of iron homeostasis.

Unified Total Synthesis of Tetracyclic Diquinane Alkaloids (+)-Paniculatine, (-)-Magellanine, and (+)-Magellaninone.

A unified route for the total synthesis of three tetracyclic diquinane alkaloids (+)-paniculatine, (-)-magellanine, and (+)-magellaninone has been accomplished in 13-14 overall steps based on late-stage diverse transformations from an advanced tetracyclic common intermediate. In the established synthesis, quick formation of the two five-membered rings was efficiently achieved by an intramolecular reductive coupling of ketone-carbonyl and ester-carbonyl and an organocatalytic intramolecular Michael addition of aldehyde-derived enamine to an internal enone functionality with satisfactory redox and step economies and excellent stereoselectivities, providing the requisite tricyclic carbo-framework possessing multiple dense stereogenic centers, and an intramolecular reductive amination finally furnished the essential piperidine ring.

Total Synthesis of Suberitines A-D Featuring Tunable Biomimetic Late-Stage Oxidative Dearomatization and Acetalization.

Aaptaminoids are a unique family of marine alkaloids bearing a benzo[de][1,6]-naphthyridine core. This work describes the first total synthesis of suberitines A-D (1-4), four typical dimeric natural aaptaminoids, employing a step-saving bidirectional strategy. Key methods applied in the total synthesis include a cationic cascade to construct the bis-isoquinoline(s) with Hendrickson reagent-mediated Friedel-Crafts-type cyclization and eliminative aromatization, and a Bronsted acid-promoted Vilsmeier cyclization to generate the naphthyridine(s).

Spatially Confined Synthesis of SnSe Spheres Encapsulated in N, Se Dual-Doped Carbon Networks toward Fast and Durable Sodium Storage.

On account of the high theoretical capacity and preferable electrochemical reversibility, tin selenides have emerged as potential anode materials in the field of sodium ion batteries (SIBs). Unfortunately, the large volume changes, low electrical conductivity, and shuttling effect of polyselenides have impeded their real application. In this work, we present a spatially confined reaction approach for controllable fabrication of SnSe spheres, which are embedded in polydopamine (PDA)-derived N, Se dual-doped carbon networks (SnSe@NSC) through a one-step carbonization and selenization method.

Azaphilones as Activation-Free Primary-Amine-Specific Bioconjugation Reagents for Peptides, Proteins and Lipids.

Residue-selective bioconjugation methods for biomolecules are highly sought to expand the scope of their biological and medical applications. Inspired by the mechanism of the generation of natural vinylogous γ-pyridones (vPDNs), we have developed a novel unique azaphilone-based, activation-free primary-amine-selective bioconjugation method for biomolecules. Our strategy allows facile functionalization of primary amine groups in peptides and proteins, including the clinically used therapeutic antibody trastuzumab, by generating a highly stable vPDN linkage.

Confined Polysulfides in N-Doped 3D-CNTs Network for High Performance Lithium-Sulfur Batteries.

Improving the utilization efficiency of active materials and suppressing the dissolution of lithium polysulfides into the electrolyte are very critical for development of high-performance lithium-sulfur batteries. Herein, a novel strategy is proposed to construct a three-dimensional (3D) N-doped carbon nanotubes (CNTs) networks to support lithium polysulfides (3D-NCNT-LiS) as a binder-free cathode for high-performance lithium-sulfur batteries. The 3D N-doped CNTs networks not only provide a conductive porous 3D architecture for facilitating fast ion and electron transport but also create void spaces and porous channels for accommodating active sulfur.

Effect of NaOH molarities to the microstructure and sodium storage performance of the Sn-MOF derived SnOmicroporous rod.

In this study, we demonstrated a facile method to prepare a novel SnOmicroporous rod with various microstructures by controlling NaOH molarities in precursor synthesis processes. Four different molarities of NaOH solution (0.005 M, 0.

Concise Unified Access to (-)-8-Deoxy-13-dehydroserratinine, (+)-Fawcettimine, (+)-Fawcettidine, and (-)-8-Deoxyserratinine Using a Direct Intramolecular Reductive Coupling.

A short, scalable, and collective total synthesis of four fawcettimine-type alkaloids in eight or nine steps is disclosed. A dense multi-small-ring -α-aminocyclopentanone successfully served as the key intermediate, which was directly accessed by a LiDBB-mediated intramolecular reductive coupling of the aliphatic imine and an ester-carbonyl. Compared to those that employ classical Heathcock intermediate(s) containing a nine-membered ring, the new strategy shows the significant improvement of the synthetic step and redox economies as well as excellent stereochemical control.