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Polyferrocene is significantly more rigid than ferrocene as evident from the 5-fold increase in its bulk modulus. Pressure dependent Raman spectra show a clear onset of polymerization in Fc at P = 220 GPa. Higher mechanical strength coupled with its metallicity makes p-Fc an interesting candidate for high pressure synthesis.A general, efficient, and substrate-controlled regiodivergent trifluoroacetylation of carbazoles has been developed through Friedel-Crafts acylation. This strategy was applicable to a wide scope of readily available substituted carbazoles at air atmosphere without using a metal catalyst, affording the corresponding trifluoroacetylated carbazoles in up to 99% yield. The divergency of the products and the orientation rules have been illustrated based on different substituents on carbazole rings. This method could also be extended to the synthesis of chlorodifluoroacetylated and pentafluoropropionylated carbazoles, which have been achieved for the first time.Extract from balloon flower root (Platycodi radix) containing platycosides as saponins is a beneficial food additive and is used for their savory taste and the alleviation of respiratory diseases. Deglycosylated platycosides show greater pharmacological effects than glycosylated platycosides. However, there are no reports on the conversion of glycosylated platycosides into deapiosylated platycosides. In this study, we showed that the crude enzyme from Rhizopus oryzae, a generally recognized as safe (GRAS) fungus isolated from meju (fermented soybean brick), completely converted glycosylated platycosides in Platycodi radix extract into deapiosylated platycosides deapiosylated platycodin D (deapi-PD), deapiosylated platycodin A (deapi-PA), deapiosylated polygalacin D (deapi-PGD), and deapiosylated platyconic acid A (deapi-PCA). Among these, deapi-PA and deapi-PCA were first identified using liquid chromatography/mass spectrometry. The anti-inflammatory and antioxidant effects of deapiosylated platycosides were greater than those of the precursor glycosylated platycosides. These deapiosylated platycosides could improve the properties of functional food additives.DNA-histone interaction is always perturbed by epigenetic regulators to regulate gene expression. Direct visualization of this interaction is yet to be achieved. By using high-speed atomic force microscopy (HS-AFM), we have observed the dynamic DNA-histone H2A interaction. HS-AFM movies demonstrate the globular core and disordered tail of H2A. PTEN inhibitor DNA-H2A formed the classic "beads-on-string" conformation on poly-l-lysine (PLL) and lipid substrates. Notably, a short-linearized double-stranded DNA (dsDNA), resembling an inchworm, wrapped around a single H2A protein only observed on the lipid substrate. Such a phenomenon does not occur for plasmid DNA or linearized long dsDNA on the same substrate. Strong adsorption of PLL substrate resulted in poor dynamic DNA-H2A interaction. Nonetheless, short-linearized dsDNA-H2A formed stable wrapping with a "diamond ring" topology on the PLL substrate. Reversible liquid-liquid phase separation (LLPS) of the DNA-H2A aggregate was visualized by manipulating salt concentrations. Collectively, our study suggest that HS-AFM is feasible for investigating epigenetically modified DNA-histone interactions.Thirteen tetrahydroxanthone dimers, atrop-ascherxanthone A (1), ascherxanthones C-G (2-6), and confluxanthones A-G (7-13), were isolated from the entomopathogenic fungus Aschersonia confluens BCC53152. The chemical structures were determined based on analysis of NMR spectroscopic and mass spectrometric data. The absolute configurations of compounds 1 and 7 were confirmed by single-crystal X-ray diffraction experiments, while the configurations of other compounds were assigned based upon evidence from NOESY and NOEDIFF experiments, modified Mosher's method, and ECD spectroscopic data together with biogenetic considerations. Compounds 1, 3-5, 7-11, and 13 showed antimalarial activity against Plasmodium falciparum (K1, multidrug-resistant strain) (IC50 0.6-6.1 μM), antitubercular activity against Mycobacterium tuberculosis H37Ra (MIC 6.3-25.0 μg/mL), and cytotoxicity against NCI-H187 (IC50 0.5-3.5 μM) and Vero (IC50 0.9-6.1 μM) cells. All tested compounds except for compound 9 exhibited cytotoxicity against KB cells (IC50 1.3-9.7 μM).Reaction of 3-hydroxy-2-pyrones with nitroalkenes bearing ester groups gives benzofuranones. The reaction allows regioselective preparation of the benzofuranones with programmable substitution at any position. link2 Complex substitution patterns are readily created. The substituted benzofuranones can be converted to substituted benzofurans.In this study, we report the design and synthesis of a series of novel thiophene-arylamide compounds derived from the noncovalent decaprenylphosphoryl-β-d-ribose 2'-epimerase (DprE1) inhibitor TCA1 through a structure-based scaffold hopping strategy. Systematic optimization of the two side chains flanking the thiophene core led to new lead compounds bearing a thiophene-arylamide scaffold with potent antimycobacterial activity and low cytotoxicity. Compounds 23j, 24f, 25a, and 25b exhibited potent in vitro activity against both drug-susceptible (minimum inhibitory concentration (MIC) = 0.02-0.12 μg/mL) and drug-resistant (MIC = 0.031-0.24 μg/mL) tuberculosis strains while retaining potent DprE1 inhibition (half maximal inhibitory concentration (IC50) = 0.2-0.9 μg/mL) and good intracellular antimycobacterial activity. In addition, these compounds showed good hepatocyte stability and low inhibition of the human ether-à-go-go related gene (hERG) channel. The representative compound 25a with acceptable pharmacokinetic property demonstrated significant bactericidal activity in an acute mouse model of tuberculosis. Moreover, the molecular docking study of template compound 23j provides new insight into the discovery of novel antitubercular agents targeting DprE1.Electrochemical CO2 reduction (CO2RR) using renewable energy sources represents a sustainable means of producing carbon-neutral fuels. Unfortunately, low energy efficiency, poor product selectivity, and rapid deactivation are among the most intractable challenges of CO2RR electrocatalysts. Here, we strategically propose a "two ships in a bottle" design for ternary Zn-Ag-O catalysts, where ZnO and Ag phases are twinned to constitute an individual ultrafine nanoparticle impregnated inside nanopores of an ultrahigh-surface-area carbon matrix. Bimetallic electron configurations are modulated by constructing a Zn-Ag-O interface, where the electron density reconfiguration arising from electron delocalization enhances the stabilization of the *COOH intermediate favorable for CO production, while promoting CO selectivity and suppressing HCOOH generation by altering the rate-limiting step toward a high thermodynamic barrier for forming HCOO*. Moreover, the pore-constriction mechanism restricts the bimetallic particles to nanosized dimensions with abundant Zn-Ag-O heterointerfaces and exposed active sites, meanwhile prohibiting detachment and agglomeration of nanoparticles during CO2RR for enhanced stability. The designed catalysts realize 60.9% energy efficiency and 94.1 ± 4.0% Faradaic efficiency toward CO, together with a remarkable stability over 6 days. Beyond providing a high-performance CO2RR electrocatalyst, this work presents a promising catalyst-design strategy for efficient energy conversion.Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C-C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels-Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio-, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diborylnorbornenes. The utility of the gem-diborylnorbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Additionally, these polymers have been successfully submitted to postpolymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.The widespread implementation of H2 as a fuel is currently hindered by the high pressures or cryogenic temperatures required to achieve reasonable storage densities. In contrast, the realization of materials that strongly and reversibly adsorb hydrogen at ambient temperatures and moderate pressures could transform the transportation sector and expand adoption of fuel cells in other applications. To date, however, no adsorbent has been identified that exhibits a binding enthalpy within the optimal range of -15 to -25 kJ/mol for ambient-temperature hydrogen storage. Here, we report the hydrogen adsorption properties of the metal-organic framework (MOF) V2Cl2.8(btdd) (H2btdd, bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which features exposed vanadium(II) sites capable of backbonding with weak π acids. Significantly, gas adsorption data reveal that this material binds H2 with an enthalpy of -21 kJ/mol. This binding energy enables usable hydrogen capacities that exceed that of compressed storage under the same operating conditions. The Kubas-type vanadium(II)-dihydrogen complexation is characterized by a combination of techniques. link3 From powder neutron diffraction data, a V-D2(centroid) distance of 1.966(8) Å is obtained, the shortest yet reported for a MOF. Using in situ infrared spectroscopy, the H-H stretch was identified, and it displays a red shift of 242 cm-1. Electronic structure calculations show that a main contribution to bonding stems from the interaction between the vanadium dπ and H2 σ* orbital. Ultimately, the pursuit of MOFs containing high densities of weakly π-basic metal sites may enable storage capacities under ambient conditions that far surpass those accessible with compressed gas storage.The highly regioselective N-alkylation reaction of 2-pyridones was achieved through hydrazone chemistry, especially for substrates with bulky secondary alkyl groups. Described herein is a copper-catalyzed coupling reaction of pyridone derivatives with tosylhydrazones.Molten hydroxides, often used for crystal growth and nanoparticle synthesis, have recently been applied for the single step densification of several inorganic materials under moderate uniaxial pressures and 1000 °C below their usual sintering temperatures. The latter approach, termed cold sintering process (CSP), is a mechanochemically driven process that enables the densification of inorganic materials through a dissolution-precipitation creep mechanism. In this study, we report the main densification mechanisms of BaTiO3 in a NaOH-KOH eutectic mixture. A chemical insight at the atomistic level, investigated by ReaxFF molecular dynamics simulations, offers plausible ionic complex formation scenarios and reactions at the BaTiO3/molten hydroxide interface, enabling the dissolution-precipitation reactions and the subsequent cold sintering of BaTiO3.
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