Halogenation-induced C-N bond activation enables the synthesis of 1,2--aryl furanosides deaminative cyclization.

1,2--Aryl furanosides are prevalent in nature and exhibit significant biological activities. The 1,2- configuration is less favorable in terms of stereoelectronic and steric effects, making the synthesis of this type of skeleton highly challenging. Traditional methods for the synthesis of 1,2--aryl furanosides usually require complicated protection manipulations, resulting in lengthy synthetic routes and low overall efficiency.

Three-dimensional covalent organic framework-based artificial interphase layer endows lithium metal anodes with high stability.

To gain a deeper understanding and address the scientific challenges of lithium dendrite growth, a robust solid-state electrolyte interface (SEI) with good mechanical properties and rapid ion conduction is crucial for the advancement of lithium metal batteries. Artificial SEI layers based on organic polymers, such as covalent organic frameworks (COF), have garnered widespread attention due to their flexible structural design and tunable functionality. In this work, a COF with 3D spatial geometric symmetry and a fully covalent topology was synthesized and used as artificial SEI layers.

Effects of current density on Zn reversibility.

Aqueous zinc (Zn) batteries (AZBs) exhibit potential as viable candidates for stationary energy storage. Improvements in the plating/stripping efficiency and lifespan of Zn anodes at high applied current density () render AZBs attractive for rapid charge and discharge scenarios. However, the existing literature presents inconsistent experimental results and interpretations regarding the impact of on Zn reversibility.

Methane C(sp)-H bond activation by water microbubbles.

Microbubble-induced oxidation offers an effective approach for activating the C(sp)-H bond of methane under mild conditions, achieving a methane activation rate of up to 6.7% per hour under optimized parameters. In this study, microbubbles provided an extensive gas-liquid interface that promoted the formation of hydroxyl (OH˙) and hydrogen radicals (H˙), which facilitated the activation of methane, leading to the generation of methyl radicals (CH˙).

Solvation structure dependent ion transport and desolvation mechanism for fast-charging Li-ion batteries.

The solvation structures of Li in electrolytes play prominent roles in determining the fast-charging capabilities of lithium-ion batteries (LIBs), which are in urgent demand for smart electronic devices and electric vehicles. Nevertheless, a comprehensive understanding of how solvation structures affect ion transport through the electrolyte bulk and interfacial charge transfer reactions remains elusive. We report that the charge transfer reaction involving the desolvation process is the rate-determining step of the fast charging when ion conductivity reaches a certain value as determined by investigating electrolytes with eight conventional solvents (linear/cyclic carbonate/ether).

Unleashing the potential of Li-O batteries with electronic modulation and lattice strain in pre-lithiated electrocatalysts.

Efficient catalysts are indispensable for overcoming the sluggish reaction kinetics and high overpotentials inherent in Li-O batteries. However, the lack of precise control over catalyst structures at the atomic level and limited understanding of the underlying catalytic mechanisms pose significant challenges to advancing catalyst technology. In this study, we propose the concept of precisely controlled pre-lithiated electrocatalysts, drawing inspiration from lithium electrochemistry.

Sialylation-induced stabilization of dynamic glycoprotein conformations unveiled by time-aligned parallel unfolding and glycan release mass spectrometry.

Sialylation, a critical post-translational modification, regulates glycoprotein structure and function by tuning their molecular heterogeneity. However, characterizing its subtle and dynamic conformational effects at the intact glycoprotein level remains challenging. We introduce a glycoform-resolved unfolding approach based on a high-throughput ion mobility-mass spectrometry (IM-MS) platform.

Recent progress in high-voltage P2-Na TMO materials and their future perspectives.

P2-type layered materials (Na TMO) have become attractive cathode electrodes owing to their high theoretical energy density and simple preparation. However, they still face severe phase transition and low conductivity. Current research on Na TMO is mostly focused on the modification of bulk materials, and the application performances have been infrequently addressed.

Dicobalt(ii) helices kill colon cancer cells enantiomer-specific mechanisms; DNA damage or microtubule disruption.

Highly diastereoselective self-assembly reactions give both enantiomers (Λ and Δ) of anti-parallel triple-stranded bimetallic Co(ii) and Co(iii) cationic helices, without the need for resolution; the first such reaction for Co. The complexes are water soluble and stable, even in the case of Co(ii). Studies in a range of cancer and healthy cell lines indicate high activity and selectivity, and substantial differences between enantiomers.

Enhanced bone regeneration by osteoinductive and angiogenic zein/whitlockite composite scaffolds loaded with levofloxacin.

Promoting angiogenesis following biomaterial implantation is essential to bone tissue regeneration. Herein, the composite scaffolds composed of zein, whitlockite (WH), and levofloxacin (LEVO) were fabricated to augment bone repair by facilitating osteogenesis and angiogenesis. First, three-dimensional composite scaffolds containing zein and WH were prepared using the salt-leaching method.

Thermodynamic evaluations of the acceptorless dehydrogenation and hydrogenation of pre-aromatic and aromatic N-heterocycles in acetonitrile.

N-heterocycles are important chemical hydrogen-storage materials, and the acceptorless dehydrogenation and hydrogenation of N-heterocycles as organic hydrogen carriers have been widely studied, with the main focus on the catalyst synthesis and design, investigation of the redox mechanisms, and extension of substrate scope. In this work, the Gibbs free energies of the dehydrogenation of pre-aromatic N-heterocycles (YH) and the hydrogenation of aromatic N-heterocycles (Y), , Δ(YH) and Δ(Y), were derived by constructing thermodynamic cycles using Hess' law. The thermodynamic abilities for the acceptorless dehydrogenation and hydrogenation of 78 pre-aromatic N-heterocycles (YH) and related 78 aromatic N-heterocycles (Y) were well evaluated and discussed in acetonitrile.

Organocatalytic atroposelective synthesis of axially chiral ,'-pyrrolylindoles indole formation.

The first organocatalytic atroposelective synthesis of axially chiral ,'-pyrrolylindoles based on -alkynylanilines was successfully established indole formation catalyzed by chiral phosphoric acid (CPA). This new synthetic strategy introduced CPA-catalyzed asymmetric 5- cyclization of new well-designed -alkynylanilines containing a pyrrolyl unit, resulting in a wide range of axially chiral ,'-pyrrolylindoles in high yields with exclusive regioselectivity and excellent enantioselectivity (up to 99% yield, >20 : 1 rr, 95 : 5 er). Considering the potential biological significance of N-N atropisomers, preliminary biological activity studies were performed and revealed that these structurally important ,'-pyrrolylindoles had a low IC value with promising impressive cytotoxicity against several kinds of cancer cell lines.

Photo-caged 2-butene-1,4-dial as an efficient, target-specific photo-crosslinker for covalent trapping of DNA-binding proteins.

Covalent trapping of DNA-binding proteins photo-crosslinking is an advantageous method for studying DNA-protein interactions. However, traditional photo-crosslinkers generate highly reactive intermediates that rapidly and non-selectively react with nearby functional groups, resulting in low target-capture yields and high non-target background capture. Herein, we report that photo-caged 2-butene-1,4-dial (PBDA) is an efficient photo-crosslinker for trapping DNA-binding proteins.

Chiral -difluoroalkyl reagents: -difluoroalkyl propargylic borons and -difluoroalkyl α-allenols.

Chiral fluorinated reagents provide new opportunities for the discovery of drugs and functional materials because the introduction of a fluorinated group significantly alters a molecule's physicochemical properties. Chiral -difluoroalkyl fragments (R-CF-C*) are key motifs in many drugs. However, the scarcity of synthetic methods and types of chiral -difluoroalkyl reagents limits the applications of these compounds.

Salt-stabilized alkylzinc pivalates: versatile reagents for cobalt-catalyzed selective 1,2-dialkylation.

The construction of Csp-Csp bonds through Negishi-type reactions using alkylzinc reagents as the pronucleophiles is of great importance for the synthesis of pharmaceuticals and agrochemicals. However, the use of air and moisture sensitive solutions of conventional alkylzinc halides, which show unsatisfying reactivity and limitation of generality in twofold Csp-Csp cross-couplings, still represents drawbacks. We herein report the first preparation of solid and salt-stabilized alkylzinc pivalates by OPiv-coordination, which exhibit enhanced stability and a distinct advantage of reacting well in cobalt-catalyzed difluoroalkylation-alkylation of dienoates, thus achieving the modular and site-selective installation of CF- and Csp-groups across double bonds in a stereoretentive manifold.

Practical synthesis of allylic amines nickel-catalysed multicomponent coupling of alkenes, aldehydes, and amides.

Molecules with an allylic amine motif provide access to important building blocks and versatile applications of biologically relevant chemical space. The need for diverse allylic amines requires the development of increasingly general and modular multicomponent reactions for allylic amine synthesis. Herein, we report an efficient catalytic multicomponent coupling reaction of simple alkenes, aldehydes, and amides by combining nickel catalysis and Lewis acid catalysis, thus providing a practical, environmentally friendly, and modular protocol to build architecturally complex and functionally diverse allylic amines in a single step.

Conformationally confined three-armed supramolecular folding for boosting near-infrared biological imaging.

Herein, a triphenylamine derivative (TP-3PY) possessing 4-(4-bromophenyl)pyridine (PY) as an electron-accepting group and tris[-(4-pyridylvinyl)phenyl]amine (TPA) with large two-photon absorption cross-sections as an electron-donating group was obtained, and showed intense absorption in the visible light region ( = 509 nm) and weak near-infrared (NIR) fluorescence emission at 750 nm. After complexation with cucurbit[8]uril (CB[8]), TP-3PY showed bright NIR fluorescence emission at 727 nm and phosphorescence emission at 800 nm. When the supramolecular assembly (TP-3PY⊂CB[8]) further interacted with dodecyl-modified sulfonatocalix[4]arene (SC4AD), the fluorescence and phosphorescence emissions were further enhanced at 710 and 734 nm, respectively.

Macrocyclization remote -selective C-H olefination using a practical indolyl template.

The synthesis of macrocyclic compounds with different sizes and linkages remains a great challenge transition metal-catalysed intramolecular C-H activation. Herein, we disclose an efficient macrocyclization strategy Pd-catalysed remote -C-H olefination using a practical indolyl template. This approach was successfully employed to access macrolides and coumarins.

Site-specific chirality-conferred structural compaction differentially mediates the cytotoxicity of Aβ42.

Growing evidence supports the confident association between distinct amyloid beta (Aβ) isoforms and Alzheimer's Disease (AD) pathogenesis. As such, critical investigations seeking to uncover the translational factors contributing to Aβ toxicity represent a venture of significant value. Herein, we comprehensively assess full-length Aβ42 stereochemistry, with a specific focus on models that consider naturally-occurring isomerization of Asp and Ser residues.

Organocatalytic intramolecular (4 + 2) annulation of enals with ynamides: atroposelective synthesis of axially chiral 7-aryl indolines.

Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis of axially chiral molecules. Most of these atroposelective reactions of alkynes rely on transition-metal catalysis, and the organocatalytic approaches are largely limited to special alkynes which act as the precursors of Michael acceptors. Herein, we disclose an organocatalytic atroposelective intramolecular (4 + 2) annulation of enals with ynamides.

Quantitative evaluation of H-donating abilities of C(sp)-H bonds of nitrogen-containing heterocycles in hydrogen atom transfer reaction.

Nitrogen-containing heterocycles are an important class of antioxidants, and their reactivity and selectivity in hydrogen atom reactions have attracted significant interest from chemists. In this work, the kinetics of hydrogen atom transfer reactions from C(sp)-H bonds of 28 nitrogen-containing heterocycles, oxygen-containing heterocycles, alicyclic amines and cycloalkanes, which were denoted as XH, to the CumO˙ radical, were investigated. The characteristic physical parameter of the substrate, , the thermo-kinetic parameter Δ(XH), was determined using the kinetic equation [Δ = Δ(XH) + Δ(Y)] to quantitatively evaluate the H-donating ability of XH.

Fragile intermediate identification and reactivity elucidation in electrochemical oxidative α-C(sp)-H functionalization of tertiary amines.

The direct α-C(sp)-H functionalization of widely available tertiary amines holds promise for the rapid construction of complex amine architectures. The activation of C(sp)-H bonds through electron transfer and proton transfer by oxidants, photoredox catalysis and electrochemical oxidation have received wide attention recently. In these reactions, the direct capture and identification of the key reactive radical intermediates are technically difficult due to their short life-time.

Fine-tuning the sequential drug release of nano-formulated mutual prodrugs dictates the combination effects.

The maintenance of robust ratiometric loading of dual therapeutic agents and fine-tuning release kinetics for consistent and optimization of combination effects is vital for discovering new anticancer drug combinations and remains challenging. Smart nanomedicine strategies have been investigated for this purpose, but most of the reported strategies focus either on ratiometric delivery or on unimodal sequential release of the two different agents, which hampers effective optimization of combination effects. Herein we report a sequential drug release system based on nanoformulated mutual prodrugs constructed by the formation of ketal linkages with different acid sensitivities, thus enabling the acid-triggered release of two anticancer drugs, paclitaxel and gemcitabine, in various sequences.